BRPI0809743B1 - POLYMER COMPOSITION AND THERMOFORMED MOLDED ARTICLE - Google Patents

Abstract

“polymer composition and thermoformed molded article”. This invention relates to polymer compositions comprising at least one interpolymer of ethylene/α-olefin and branched and/or high melt strength polypropylene, methods of making the polymer compositions, and products molded, overmoulded, extruded into profiles or thermoforms made from polymer compositions. the polymer compositions may have reduced post-thermoformed or post-extruded sheet gloss properties (profiles) and/or improved scratch resistance properties.

Description

POLYMER COMPOSITION AND THERMOFORMED MOLDED ARTICLE

Field of the invention [001] This invention relates to polymer compositions comprising at least one ethylene / aolefin interpolymer and a branched and / or high melt strength polypropylene, methods for making polymer compositions, and molded products, extruded to profiles, or thermoformed made of polymer compositions. The polymer compositions may have properties of reduced post-thermoforming and reduced post-extrusion and / or improved scratch resistance.

Background to the invention [002] Each year, approximately 20 million pounds of extruded or calendered sheets are used to make parts for automotive interiors such as door panels and instrument panels in North America only. Generally, interior parts can be prepared from extruded sheets known processes for plastics, such as thermoforming. Currently, most extruded sheets are made of flexible poly (vinyl chloride) (PVC-f) and thermoplastic polyolefin (TPO), and PVC-f and TPO sheets are generally coated with polyurethane (PU) coatings to maintain low brightness of post-thermoformed parts (eg, <about 6% at 60 degrees) for consumer safety reasons and to increase scratch resistance. In general, the use of polyurethane coatings is not desirable due to the high emissions of volatile organic compounds (VOC), and interference with the replication of grain patterns in PVC-f and TPO sheets. Dai, automotive parts suppliers are always looking for

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2/126 alternative materials with low gloss. Attempts to use alternative polymer compositions such as mixtures of elastomers and polyolefins such as polypropylene are often unsatisfactory since the gloss of the extruded parts is generally high and the scratch resistance is generally low.

[003] Each year, approximately 30 million pounds of profiles using low-gloss thermoplastic vulcanizers and more than 700 million pounds of profiles are produced using high-gloss poly (vinyl chloride). There is a desire by suppliers to maintain low brightness and use lower cost alternatives. Attempts to use alternative polymer compositions such as mixtures of elastomers and polyolefins such as polypropylene are often unsatisfactory since the gloss of the extruded profile is generally high and the scratch resistance is generally low.

[004] Hence, there is a need for new polymer compositions that are thermoformable and / or extrudable to shaped profiles such as interior parts for transport industries such as the automotive industry. Specifically, there is a need for extruded sheets that (1) can be thermoformed into parts for automotive interiors that have a desired gloss of less than 6%; (2) are substantially free from defects such as entanglements, scarifications, tears, microcrateeras, and the like;

(3) exhibit improved scratch resistance; and (4) do not require PU coatings for gloss control. In addition, there is a need for parts for automotive interiors made from the new polymer compositions that

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3/126 are thermoformable and have the desired gloss properties.

Summary of the invention [005] The above needs are met by several aspects of adherence to inventions. In one aspect, the invention relates to a polymer composition comprising at least one ethylene / α-olefin interpolymer and a polypropylene. In one embodiment, polypropylene is a branched or high melt strength polypropylene. In another embodiment, the polypropylene has a melt flow rate of at least about 2, preferably at least about 2.5 g / 10 minutes measured with a load of 2.16 kg at 230 ° C according to ASTM D1238. In another embodiment, a polypropylene, preferably branched, has a delta tg value of 0.1 radian per second of less than about

2.5, preferably less than about 1.5, more preferably less than about 1.0.

[006] In another embodiment, a polypropylene, preferably branched, has a delta tg value at 0.1 radian per second of less than about 2.5, preferably less than about 1.5, more preferably less than about 1.0.

[007] In another embodiment, the ethylene / a-olefin interpolymer has an M _w / M _n of about 1.7 to about

3.5, at least one melting point, T _m , in degrees Celsius, and a density, d, in grams / cubic centimeter, with the numerical values of T _{m and} d corresponding to the relationship:

T _m > -2002.9 + 4538.5 (d) - 2422.2 (d) ² .

[008] In another embodiment, the ethylene / a-olefin interpolymer has an M _w / M _n of about 1.7 to about

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3,5, and is defined by a heat of fusion, ΔΗ in J / g, and a delta amount, ΔΤ, in degrees Celsius defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak, the values of ΔΤ and ΔΗ have the following relationships:

ΔΤ> -0.1299 (Δη) + 62.81 for Δη greater than zero up to 130 J / g,

ΔΤ> 48 ° C for ΔΗ greater than 130 J / g, the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the cumulative polymer has an identifiable peak, then the temperature CRYSTAF is 30 ° C.

[009] In another embodiment, the ethylene / a-olefin interpolymer has an elastic recovery, Re, in percentage at 300 percent elastic deformation and 1 cycle measured with a compression molded film of the ethylene / a-olefin interpolymer , and a density d, in grams per cubic centimeter, with the numerical values of Re ed satisfying the following relationship, when the ethylene / α-olefin interpolymer is substantially free of the cross-linked phase:

Re> 1481 - 1629 (d).

[010] In another embodiment, the ethylene / a-olefin interpolymer has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by the fraction having a comonomer content of at least 5 percent higher that of a comparable random ethylene interpolymer eluting between the same temperatures, the comparable random ethylene interpolymer having the same comonomer (s) and melting index, density, and molar comonomer content (based on In all the

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5/126 polymer) within 10 percent of that of the ethylene / a-olefin interpolymer.

[011] In another embodiment, the ethylene / a-olefin interpolymer is characterized by a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° CG' (100 ° C ), the ratio of G '(25 ° C) to G' (100 ° C) is from about 1: 1 to about 10: 1.

[012] In another embodiment, the ethylene / a-olefin interpolymer has at least a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF characterized by the fraction having a block index of at least 0.5 and up to about 1 and a molecular weight distribution, M _w .M _n , greater than about 1.3.

[013] In another embodiment, the ethylene / a-olefin interpolymer has an average block index greater than zero and up to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1 , 3.

[014] In another embodiment, the ethylene / α-olefin interpolymer is styrene, propylene, 1-butene, 1-hexene, [015] 4-methyl-1-pentene, norbornene, 1-decene, 1,5hexadiene, or combinations of these.

[016] The characteristics of the ethylene / aolefin interpolymer above are given with respect to the ethylene / a-olefin interpolymer before any significant crosslinking, i.e., before crosslinking. The ethylene / α-olefin interpolymers useful in the present invention may or may not be cross-linked to such a degree as to obtain the desired properties. Using the above characteristics as measured before crosslinking, it is not intended to suggest whether or not the interpolymer is required to be crosslinked - only that the

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6/126 characteristic is measured with respect to the interpolymer without significant crosslinking. The crosslinking may or may not modify each of these properties depending on the specific polymer and the degree of crosslinking. In another aspect, the invention relates to articles such as thermoformed articles comprising the polymer composition disclosed herein. In one embodiment, the thermoformed article is an article for the transport industry, such as the interior or exterior of an automotive vehicle. In another embodiment, the gloss at 60 degrees of the surface of the thermoformed article is less than 9.0%. And another embodiment, there is no visible whitening on the surface of the thermoformed article after being tested for scratches according to ASTM D7027-05 at a load equal to or less than 20 N and a scratch speed of 50 mm / s.

[017] In another embodiment, the thermoformed polymer or article composition further comprises at least one additive, the additive being selected from the group consisting of release agents, such as a polysiloxane, a colorant or pigment, plasticizer, an oil, an antioxidant, a UV stabilizer, a filler, a lubricant, an anti-fog agent, a flow adjuvant, a coupling agent, a cross-linking agent, a nucleating agent, a surfactant, a solvent, a flame retardant, a antistatic agent, an antimicrobial, a scratch or damage resistance agent, or a combination of these.

[018] Additional aspects of the invention and features and properties of various embodiments of the invention will become apparent with the following description.

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Brief description of the drawings [019] In the following, the invention will be described in relation to the attached drawings, in which:

[020] Figure 1 shows the melting point / density ratio for inventive polymers (represented by diamonds) compared to traditional random copolymers (represented by circles) and Ziegler-Natta copolymers (represented by triangles);

[021] Figure 2 shows DSC-CRYSTAF delta plots as a function of DSC Cast Enthalpy for various polymers. Diamonds represent random ethylene / octene copolymers; and the circles represent examples of polymers 1-4; triangles represent examples of polymers 5-9; and the circles represent examples of polymers 10-19. The symbols X represent comparative examples of polymers A * -F *;

[022] Figure 3 shows the effect of density on elastic recovery for non-oriented films made from inventive polymers (represented by squares and circles) and traditional copolymers (represented by triangles that are various AFFINITY® polymers (The Dow Chemical Company)). The squares represent inventive ethylene / butene copolymers; and the circles represent inventive ethylene / octene copolymers;

[023] Figure 4 is a plot of the octene content of ethylene / l-octene fraction fraction copied by TREF against the elution temperature for the polymer fraction of example 5 (represented by circles) and comparative polymer of the comparative examples. E * and F * (represented by the symbols X). Diamonds represent copolymers of

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8/126 traditional random ethylene / octene;

[024] Figure 5 is a plot of the octene content of ethylene / l-octene fraction fraction copied by TREF against the elution temperature of the fraction for the polymer of example 5 (curve 1) and for the polymer of the comparative example F * (curve 2). The squares represent the polymer of comparative example F *, and the triangles represent example 5;

[025] Figure 6 is a graph of the storage module log as a function of temperature for the comparative ethylene / l-octene copolymer (curve 2) and the propylene / ethylene copolymer (curve 3) and for two copolymers in ethylene / l-octene block of the invention made with different amounts of chain transfer agent (curves 1);

[026] Figure 7 shows a TMA plot (1 mm) against the flexural modulus for some inventive polymers (represented by diamonds), compared to some known polymers. The triangles represent different VERSIFY® polymers (The Dow Chemical Company), the circles different ethylene / styrene copolymers; and the squares represent several AFFINITY® polymers (The Dow Chemical Company);

[027] Figures 8A-D show optical micrographs of the surface of the extruded and thermally treated sheets of example 21 (figures 8A and 8B respectively) and comparative example M (figures 8C and 8D, respectively), taken under Nomarski's interference contrast to 200X amplification;

[028] Figures 9A-D show optical micrographs of the surface of the extruded and thermally treated sheets of the

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9/126 example 21 (figures

9A and 9B respectively) and comparative example

M (figures

9C and 9D, respectively);

[029] figure shows the algorithms provided by the software resident in the Tencor Pl-5 (v 6.41);

[030] figure shows a schematic view of a scratch testing machine used to measure scratch resistance;

[031] figure 12 shows an optical micrograph of the surface of the extruded profile of a comparative example of

Santoprene taken under Nomarski's reflected interference contrast at 150X amplification;

[032] figure shows the optical micrograph of the surface of the extruded profile of example 32 taken under Nomarski's reflected interference contrast at 200X amplification;

[033] Figure 14 shows the optical micrograph of the surface of the extruded profile of the comparative example taken under Nomarski's interference contrast at 200X amplification.

Detailed description of the invention [034]

Polymer means a polymeric material prepared by polymerizing monomers, of the same or different types. The generic term polymer encompasses the terms homopolymer, copolymer, terpolymer, as well as interpolymer.

[035]

Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes the term copolymer (which is generally used to refer to a polymer prepared from two different monomers).

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It also encompasses polymers made by polymerizing four or more types of monomers.

[036] The term ethylene / α-olefin interpolymer generally refers to polymers comprising ethylene and an α-olefin having 3 or more carbon atoms. Preferably, ethylene comprises the predominant molar fraction of the entire polymer, i.e., ethylene comprises at least about 50 mole percent of all polymer. More preferably, ethylene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial remainder of all polymer comprising at least one other comonomer which is preferably an α-olefin having 3 or more carbon atoms. For many ethylene / α-olefin copolymers, the preferred composition comprises an ethylene content greater than about 80 mole percent of all polymer and an octene content of about 10 to about 80 mole percent of all polymer and an octene content of about 10 to about 15, preferably about 15 to about 20 mole percent of the entire polymer. In some embodiments, ethylene / a-olefin interpolymers do not include those produced in low yields or in a lesser amount or as a by-product of a chemical process. While the ethylene / a-olefin interpolymers can be mixed with one or more polymers, the ethylene / a-olefin interpolymers as produced are substantially pure and often comprise a predominant component of the reaction product of a polymerization process.

[037] The term composition, as used here, includes

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11/126 a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from materials of the composition.

[038] Ethylene / α-olefin interpolymers comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by blocks or multiple segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene / α-olefin interpolymers are block interpolymers, preferably multiblock interpolymers or copolymers. The terms interpolymer and copolymer are used interchangeably here. In some embodiments, the multiblock copolymer may be represented by the following formula:

(AB) _n where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or higher, A represents a hard block or segment and B represents a soft block or segment.

Preferably,

As and Bs are connected in a substantially linear manner, as opposed to a substantially branched or substantially star-shaped manner. In other embodiments, blocks A and blocks B are randomly distributed along the polymer chain. In other words, block copolymers generally do not have a structure as follows:

AAA-AA-BBB-BB [039] In still other embodiments, block copolymers generally do not have a third type of block, which comprises different comonomer (s). In still others

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12/126 achievements, each block

A and block B have monomers or comonomers distributed substantially at random within the block.

In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of different composition, such as a tip segment, which has a substantially different composition than the rest of the block.

[040]

Multiblock polymers comprise different amounts of hard and soft segments. Hard segments refer to polymerized block units in which ethylene is present in an amount greater than about weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent based on the weight of the polymer. In some embodiments, the hard segments comprise all or substantially all ethylene. Soft segments, on the other hand, refer to blocks of polymerized block units in which the comonomer content (monomer content other than ethylene) is greater than about 5 percent, preferably greater than about 5 percent by weight, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments may be greater than about 20 weight percent, greater than about 25 weight percent, greater than about weight percent, greater than about 35 percent weight weight, greater than about weight percent, greater than about 45 weight percent, greater

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13/126 than about 50 weight percent, or greater than about 60 weight percent.

[041] The soft segments may often be present in a block interpolymer of about 1 weight percent to about 99 weight percent of the total weight

of the interpolymer in block, preferably about in 5 the fence 95 Percent in pe only, about 10 to fence 90 per percent in Weight, in fence from 15 to about 85 per percent in Weight, in fence in 20 The about 80 percent in weight of fence in 25 the fence in 75 weight percent, in about 30 to fence in 7 0 by percent in weight of about 35 to about 65

weight percent, from about 40 to about 60 weight percent, or from about 45 to about 55 weight percent of the total weight of the block copolymer. Conversely, the hard segments may be present in similar bands. The percentage by weight of hard segments and the percentage by weight of soft segments can be calculated based on data obtained by DSC or NMR. Such methods and calculations are disclosed in US Patent Application Serial No. 11 / 376,835, entitled Ethylene / a-Olefin Block Interpolymers, simultaneously filed on March 15, 2006, on behalf of Colin LP Shan, Lonnie Hazlitt, et al. , and assigned to Dow Global Technologies Inc., whose disclosure is hereby incorporated in its entirety by reference.

[042] The term crystalline, if used, refers to a polymer that has a first order transition or melting point (T _m ) or crystalline as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term semicrystalline. The term amorphous refers to a

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14/126 deficient polymer from a melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

[043] The term olefin multi-block interpolymer, multi-block copolymer or segmented copolymer refers to a polymer comprising two or more distinct segments or regions (referred to as blocks) preferably linearly linked, that is, a polymer comprising chemically differentiated units that they are joined point-to-point with respect to polymerized ethylene functionality, rather than in a pending or grafted manner. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated in it, the density, the amount of crystallinity, the size of crystallite attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regal-regularity or regal-irregularity, the amount of branching, including long-chain or hyper-branching branches, homogeneity or any other physical or chemical property. Multiblock copolymers are characterized by unique distributions of both polydispersity index (PDI or M _w / M _n ), length distribution, and / or block number distribution due to the unprecedented process of making copolymers. More specifically, when produced in a continuous process, the polymers desirably have a PDI of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2, and most preferably from 1.8 to 2.1. When produced by a batch or semi-batch process, the polymers have a PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to

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2.0, and most preferably from 1.4 to

1, 8.

[044]

In the following description, all numbers are approximate values, regardless of whether the term about or approximately is used in connection with them.

They can range from 1 percent, 2 percent, 5 percent or, sometimes, to 20 percent.

Whenever a numerical range with a lower limit, R ^L and an upper limit R ^u , is disclosed, any number falling within that range will be specifically disclosed. In particular, the following numbers within the range will be specifically

R = R ^L + k * (R ^u -R ^l ), where k is a variable ranging from released:

percent to 100 percent with an increment of 1 is 1 percent,

i. yeah, k

Percent, 2 per percent, 3 per percent, 4 per percent, 5 per percent, ..., 50 per percent, 51 per percent, 52 per percent, • · · r 95 Percent, 96 per percent, 97 per percent, 98 per percent, 99 per

cent.

percent, 100 per

In addition, any numerical range defined by two R numbers as defined above will also be specifically disclosed.

[045]

Embodiments of the invention provide a method for reducing the tendency to block and / or re-block some polymer particles, such as polyolefin pellets, and some polymer articles, such as polyolefin films. The anti-blocking polymer compositions comprise an ethylene / α-olefin interpolymer disclosed herein and an amide-based blocking agent. The ethylene / α-olefin interpolymers disclosed herein are a multi-block copolymer comprising at least one soft block and at least one hard block. The anti-blocking polymer composition may have a pellet blocking resistance equal to or less than about 4800 Pa (100 lb / ft ² ).

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In some embodiments, the pellet is equal to or less than equal to or less than 240 Pa (5 lb / ft ² ). When the composition is transformed into a film, blocking less than according to the ASTM D-3354 method.

the blocking resistance of about 2400 Pa (50 lb / ft ² ), lb / ft ² ), or about 0 Pa (0 of anti-blocking polymer is film may have a strength of 100 grams, measured by

In some embodiments, the

strength of blocking is any less what fence in 80 grams, any less what fence in 60 grams, any less what fence in 50 grams, any less what fence in 30 grams, any less what fence in 30 grams, any less what fence in 20 grams, or less what about in 10 grams. In

the blocking force is less than other embodiments, about 5 grams or zero grams.

[046] The pellet blocking force can be measured as follows: pellets (150 g) are loaded into a hollow cylinder 5 cm (2) in diameter which is made of two halves held together by a hose clamp. A load of 1.25 kg (2.75 lb) is applied to the pellets in the cylinder at 45 ° C for 3 days. After 3 days, the pellets consolidate freely as a cylindrical shaped billet. The billet is removed from the form and the blocking force is measured by loading the cylinder of compressed blocked pellets using an Instron ^MR instrument to measure the compressive force required to break the cylinder into pellets. Ethylene / a-olefin interpolymers [047] The ethylene / a-olefin interpolymers used in embodiments of the invention (also referred to as an inventive interpolymer or inventive polymer) comprise ethylene and one or more polymerizable a-olefin comonomers in the polymerized form, characterized per

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17/126 multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multi-block copolymer. Ethylene / aolefin interpolymers are characterized by one or more of the aspects described as follows.

[048] In one aspect, the ethylene / aolefin interpolymers used in embodiments of the invention have an M _w / M _n of about 1.7 to about 3.5 and at least one melting point, T _m , in degrees Celsius and a density, d, in grams per cubic centimeter, with the numerical values of the variables corresponding to the relationship:

T _m > -2002, 9 + 4538 (d) - 2422.2 (d) ² , and preferably

T _m > -6,288, 1 + 13141 (d) - 6720, 3 (d) ² , and more preferably

T _m > -858.91 - 1825.3 (d) + 1112.8 (d) ² .

[049] Such a melting point / density relationship is illustrated in figure 1. Unlike traditional random ethylene / α-olefin copolymers whose melting points decrease with decreasing densities, the inventive interpolymers (represented by diamonds) exhibit substantially independent points density fusion,

particularly when the density is between fence of 0, 87 g / cm ³ about 0.95 g / cm ³ . For example, O Score in Fusion in such polymers is in the fence range in 110 ° C The fence in 130 ° C when the density ranges from 0.875 g / cm ³ The fence in 0.945 g / cm ³ . In some achievements, O Score in Fusion in

such polymers are in the range of about 115 ° C to about 125 ° C when the density ranges from 0.875 g / cm ³ to about 0.945 g / cm ³ .

[050] In another aspect, the interpolymers of

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18/126 ethylene / a-olefin comprise, in polymerized form, ethylene and one or more α-olefins and are characterized by a ΔΤ, in degrees Celsius, defined as the temperature of the highest peak of Differential Scanning Calorimetry (DSC) less the temperature for the highest peak of Crystallization Fractionation Analysis (CRYSTAF) and a heat of fusion in J / g, ΔΗ, and ΔΤ and ΔΗ satisfy the following relationships:

ΔΤ> -0.1299 (ΔΗ) + 62.81 and preferably

ΔΤ> -0.1299 (ΔΗ) + 64.38, and more preferably

ΔΤ> -0.1299 (ΔΗ) + 65.95, for ΔΗ up to 130 J / g. In addition, ΔΤ is equal to or greater than 48 ° C for ΔΗ greater than 130 J / g. The CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak should represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C, and ΔΗ is the numerical value of the heat of fusion in J / g. More preferably, the highest CRYSTAF peak contains at least 10 percent cumulative polymer. Figure 2 shows plotted data for inventive polymers as well as comparative examples. Integrated peak areas and peak temperatures are calculated using the computerized design program provided by the instrument manufacturer. The diagonal line shown for the comparative random octene ethylene polymers corresponds to the equation ΔΤ = 0.1299 (ΔΗ) + 62.81.

[051] In yet another aspect, ethylene / a-olefin interpolymers have a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using Fractionation by

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Increasing Temperature Elution (TREF), characterized by said fraction having a higher molar content of comonomer, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a fraction of random ethylene interpolymer comparable, the comparable random ethylene interpolymer containing the same comonomer (s), and having a melt index, density, and molar comonomer content (based on the entire polymer) within 10 per percent of that of the block interpolymer. Preferably, the M _w / M _n of the comparable interpolymer is also within 10 percent of that of the block interpolymer and / or the comparable interpolymer has a total comonomer content within 10 percent of that of the block interpolymer.

[052] In yet another aspect, ethylene / a-olefin interpolymers are characterized by an elastic recovery, Re, as a percentage of 300 percent deformation and 1 cycle measured on a film molded by compression of an ethylene / interpolymer / a-olefin, and a density, d, in grams per cubic centimeter, with the values of Re ed satisfying the relationship when the ethylene / aolefin interpolymer is substantially free of the cross-linked phase: Re> 1481 - 1629 (d); and preferably

Re> 1491 - 1629 (d); and more preferably

Re> 1501 - 1629 (d); and even more preferably

Re> 1511 - 1629 (d).

[053] Figure 3 shows the effect of density on elastic recovery for unoriented films made from certain inventive interpolymers and traditional random copolymers. For the same density, interpolymers

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12/20 inventories show substantially higher elastic recoveries.

[054] In some embodiments, ethylene / a-olefin interpolymers have a tensile strength above 10 MPa, preferably a tensile strength> 11 MPa, more preferably a tensile strength> 13 MPa and / or an elongation at break at least 600 percent, more preferably at least 700 percent, highly preferably at least 800 percent, and most preferably at least 900 percent at a crosshead separation rate of 11 cm / minute.

[055] In other embodiments, ethylene / a-olefin interpolymers have (1) a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° CG' (100 ° C ) from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and / or (2) a permanent compression strain at 70 ° C of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent percent, to a permanent compression strain of 0 percent.

[056] In still other embodiments, ethylene / a-olefin interpolymers have a melting heat of less than 85 J / g and / or a pellet blocking resistance equal to or less than 4800 Pa (100 pounds / foot ² ) , preferably equal to or less than 2400 Pa (50 pounds / foot ² ), especially equal to or less than 240 Pa (5 pounds / foot ² ), and as low as 0 Pa (0 pounds / foot ² ).

[057] In some embodiments, multiblock copolymers have a PDI adjusting to the Flory distribution rather than a Poisson distribution. Copolymers

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21/126 are further characterized by having both a polydispersed block distribution and a polydispersed block size distribution and a more likely distribution of block length distribution. Preferred multiblock copolymers are those comprising 4 or more blocks or segments including end blocks. More preferably, the copolymers include at least 5, 10 or 20 blocks or segments including end blocks.

[058] The comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. In addition, for polymers or polymer mixtures having relatively wide TREF curves, the polymer is desirably first fractionated using TREF to fractions each having an eluted temperature range of 10 ° C or less. That is, each eluted fraction has a collection temperature window of 10 ° C or less. Using this technique, said block interpolymers have at least one such fraction having a higher comonomer molar content than a corresponding fraction of the comparable interpolymer.

[059] In another aspect, the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks (i.e. at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), more preferably a multi-block copolymer, said block interpolymer having a peak (but not just a molecular fraction) that elutes between

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40 ° C and 130 ° C (but without collecting and or isolating individual fractions), characterized by said peak having a comonomer content estimated by infrared spectroscopy when expanded using a maximum width / maximum mean area (FWHM) calculation, a higher average molar comonomer content, preferably at least 5 percent higher, more preferably at least 10 percent higher, than the peak of a random ethylene interpolymer comparable to the same elution temperature and expanded using an area calculation of maximum width / maximum medium (FWHM), and said comparable random ethylene interpolymer has the same comonomer (s) and has a melting index, density, and molar comonomer content (based on the polymer) within 10 percent of those of the blocked interpolymer. Preferably, the M _w / M _n of the comparable interpolymer is also within 10 weight percent of that of the blocked interpolymer and / or the comparable interpolymer has a total comonomer content within 10 of that of the blocked interpolymer. The calculation of total width / medium maximum (FWHM) is based on the response area ratio of methyl to methylene [CH3 / CH2] of the ATREF infrared detector, with the highest (largest) peak being identified from the line base, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between Ti and T ₂ , where Ti and T ₂ are points determined to the left and right of the ATREF peak, dividing the height of the peak by two, and then drawing a horizontal line to the baseline that intersects the right and left portions of the ATREF curve. A calibration curve for comonomer content is made using copolymers of

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23/126 random ethylene / a-olefin, plotting the ratio of comonomer content per NMR against FWHM of the TREF peak. For this infrared method, the calibration curve is generated for the same type of comonomer of interest. The TREF peak comonomer content of the inventive polymer can be determined by referencing this calibration curve using its methyl area: methylene ratio [CH3 / CH2] of the TREF peak.

[060] The comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance spectroscopy being preferred. Using this technique, said blocked interpolymers have a higher comonomer content than a comparable comparable interpolymer.

[061] Preferably, for ethylene and 1-octene interpolymers, the block interpolymer has a comonomer content of the TREF fraction eluting between 40 ° C and 130 ° C greater than or equal to the amount (-0,2013) T + 20.07, more preferably greater than or equal to the amount of (-0,2013) T + 21.07, where T is the numerical value of the peak elution temperature of TREF being compared, measured in ° C.

[062] Figure 4 shows graphically an embodiment of the ethylene and 1-octene block interpolymers where a plot of the comonomer content against the elution temperature of TREF for several comparable ethylene / loctene interpolymers (random copolymers) is adjusted to a line representing (-0,2013) T + 20.07 (solid line). The line for the equation (-0,2013) T + 21.07 is shown by a dotted line. Also shown are comonomer contents for fractions of various block ethylene / l-octene interpolymers of the invention (multi-block copolymers). Every

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24/126 fractions of the block interpolymer have substantially higher 1-octene contents than any of the lines at equivalent elution temperatures. This result is characteristic of the inventive interpolymer and is believed to be due to the presence of differentiated blocks within the polymer chains, having both crystalline and amorphous nature.

[063] Figure 5 shows graphically the TREF curve and the comonomer content of polymer fractions for example 5 and comparative F to be discussed below. The peak eluting from 40 to 130 ° C, preferably from 60 ° C to 95 ° C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than 10 ° C. Effective data for example 5 is represented by triangles. Those skilled in the art will appreciate that an appropriate calibration curve can be constructed for interpolymers comprising different comonomers and a line used as a comparison adjusted to the TREF values obtained from their comparative interpolymers.

monomers, preferably random copolymers made using a metallocene or other catalyst composition homogeneous. The inventive interpolymers are characterized

by a molar content of comonomer greater than the value determined from the calibration curve at the same elution temperature, preferably at least 5 percent higher, more preferably at least 10 percent higher.

[064] In addition to the aspects and properties described here, the inventive polymers may be characterized by one or more additional characteristics. In one aspect, the inventive polymer is an interpolymer of

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25/126 olefin, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by blocks or multiple segments of two or more polymerized monomer units differing in physical or chemical properties (blocked interpolymer), more preferably a multiblock copolymer, said block interpolymer having a molecular fraction eluting between 40 ° C and 130 ° C, when fractioned using TREF increments, characterized in that said fraction has a higher molar content of comonomer, preferably at least 5 percent, more preferably at minus 10, 15, 20 or 25 percent or greater than that of a fraction of comparable random ethylene interpolymer eluting between the same temperatures, said comparable random ethylene interpolymer comprising the same comonomer (s) ( s), preferably it is (are) the same comonomer (s) and a melting index, density, and molar content of how number (based on the entire polymer) within 10 percent of that of the blocked interpolymer. Preferably, the M _w / M _n of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and / or the comparable interpolymer has a total comonomer content within 10 percent of that of the blocked interpolymer.

[065] Preferably, the above interpolymers are ethylene interpolymers and at least one α-olefin, especially those interpolymers having an overall polymer density of about 0.855 to about 0.935 g / cm ³ , and more especially for polymers having more than about 1 percent by weight of comonomer, the blocked interpolymer having a comonomer content of the TREF fraction eluting

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26/126 between 40 and 130 ° C greater than or equal to the amount of (0.1356) T + 13.89, more preferably greater than or equal to the amount of (-0.1356) T + 14.93, and the more preferably greater than or equal to the amount of (-0,2013) T + 21.07, where T is the numerical value of the elution temperature of ATREF peak of the fraction being compared, measured in ° C.

[066]

Preferably, for the above ethylene interpolymers and at least one α-olefin, especially those interpolymers having an overall polymer density of about 0.855 to about

0.935 g / cm ³ 'and more especially for polymers having more than about molar percent of comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 ° C greater than or equal to the amount ( -0,2013) T + 20.07, more preferably greater than or equal to the quantity (-0,2013) T +

21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in ° C.

[067] In yet another aspect, the inventive polymer is an olefin interpolymer, preferably containing ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical properties or physical (blocked polymer), more preferably a multiblock polymer, said block interpolymer having a molar fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF increments, characterized in that each fraction has a hair comonomer content minus 6 molar percent, having a melting point greater than about 100 ° C. For those fractions having a comonomer content of about 3 molar percent to about 6 percent

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27/126 molar percent, each fraction having a DSC melting point of about 110 ° C or higher. More preferably, said polymer fractions having at least 1 mole percent monomer, have a melting point by DSC that corresponds to the equation:

T _m > (-5.5926) (moles% comonomer in the fraction) + 135.90.

[068] In yet another aspect, the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical properties or physical (blocked interpolymer), more preferably a multi-block copolymer, said block interpolymer having a molar fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF increments, characterized in that each fraction has an ATREF elution temperature greater than or equal to about 76 ° C, have a melting enthalpy (heat of melting) as measured by DSC corresponding to the equation:

Heat of Fusion (J / g) <(3.1718) (ATREF elution temp. In ° C) -136.58.

[069] The inventive block interpolymers have a molecular fraction that elutes between 40 ° C and 130 ° C, when fractioned using TREF increments, characterized in that each fraction has an ATREF temperature between 40 ° C and less than about 76 ° C, have a melting enthalpy (heat of melting) as measured by DSC corresponding to the equation:

Heat of Fusion (J / g) <(1.1312) (ATREF elution temp. In ° C) +22.97. Measurement of ATREF Peak Comonomer Composition by Infrared Detector [070] The composition of the TREF peak comonomer may

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28/126 be measured using a commercially available IR4 infrared detector from Polymer Char, Valencia, Spain (http // www.polymerchar.com).

[071] The detector's composition mode is equipped with a measurement sensor (CH ₂ ) and a composition sensor (CH ₃ ) which are fixed narrowband infrared filters in the 2800-300 cm ^{-1 region} . The measurement sensor detects the methylene carbons (CH ₂ ) in the polymer (which is directly related to the concentration of the polymer in the solution) while the composition sensor detects the methyl groups (CH ₃ ) of the polymer. The mathematical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the comonomer content of the polymer measured in solution and its response is calibrated with known ethylene alpha-olefin copolymer standards.

[072] The detector when used with an ATREF instrument provides both a concentration (CH ₂ ) and composition (CH ₃ ) response signal from the polymer eluted during the TREF process. A specific polymer calibration can be created by measuring the area ratio of CH ₃ to CH ₂ for polymers with known comonomer content (preferably measured by NMR). The comonomer content of a polymer's ATREF peak can be estimated by applying a reference calibration of the area ratio to the individual CH ₃ and CH ₂ response (i.e., the CH ₃ / CH ₂ ratio against comonomer content ).

[073] The peak area can be calculated using a maximum total / medium width (FWHM) calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram. The calculation of maximum total / medium width is based on the response area ratio of methyl to methylene [CH ₃ / CH ₂ ] of the infrared detector

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29/126 of ATREF, with the highest (highest) peak being identified from the baseline, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between Ti and T ₂ , where Ti and T ₂ are points determined to the left and right of the ATREF peak, dividing the height of the peak by two, and then drawing a horizontal line to the baseline that intersects the right and left portions of the ATREF curve.

[074] The application of infrared spectroscopy to measure the comonomer content of polymers in this method of

ATREF-infrared is, in principle, similar to that of GPC / FTIR systems as described in the following references: Markovitch, Ronald P .; Hazlitt, Lonnie G .;

Smith, Linley; Development of gel-permeation chromatographyFourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers. Polymeric Materials Science and Engineering (1991), 65, 98-100; and Deslauriers, P.J .; Rohlfing, D.C .; Shieh, E.T .; Quantifying short chain branching microstructures in ethylene-l-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR), Polymer (2002), 43, 59170, both of which are incorporated herein by reference.

[075] In other embodiments, the inventive ethylene / a-olefin interpolymer is characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3. The average block index, ABI, is the weighted average of the block index (BI) for each of the fractions obtained by preparative TREF of 20 ° C and 110 ° C, with an increase of 5 ° C ':

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ΑΒΙ = ZtfWiBIi) where Bli is the block index for the nth fraction of the ethylene / a-olefin interpolymer obtained by preparative TREF, and w ± is the weight percentage of the nth fraction. [076] For each polymer fraction, BI is defined by one of the following equations (both of which give the same BI value):

1 / Τχ - l / Τχο LnP _x - LnPxo

BI = ------------ or BI = ----------- 1 / Ta - 1 / Tab LuPa - LiiPab where T _x is the elution temperature of preparative ATREF for the ith fraction (preferably expressed in Kelvin), P _x is the molar fraction of ethylene for the ith fraction, which can also be measured by NMR or IR as described above. P _AB is the molar fraction of ethylene for the entire ethylene / a-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. T _A and P _A are the elution temperature and the molar fraction of ethylene for pure hard segments (which refer to the crystalline segments of the interpolymer). As a first order approximation, the values of T _A and P _A are adjusted to those for a high density polyethylene homopolymer, if the effective values for the hard segments are not available. For calculations performed here, T _A is 372 ° K, P _A is 1.

[077] T _AB is the ATEF temperature for a random copolymer of the same composition and having a molar ethylene fraction of P _AB . T _AB can be calculated from the following equation:

LnP _AB = α / Τ _ΑΒ + B where α and B are two constants that can be determined by calibration using a number of random copolymers

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12/31 known. It should be noted that a and B may vary from instrument to instrument. In addition, it would be necessary to create your own calibration curves with the composition of interest and also in a similar molecular weight range as the fractions. There is a slight effect by molecular weight. If the calibration curve is obtained from similar molecular weight ranges, such an effect may be essentially negligible. In some embodiments, random ethylene copolymers satisfy the following relationship:

Ln P = -237.83 / T _atref + 0.639

Τχο is the ATREF temperature for a random copolymer of the same composition and having a molar ethylene fraction of P _x . Τχο can be calculated from LnP _x = a / T _x0 + β. Conversely, P _X o is the molar fraction of ethylene for a random copolymer of the same composition and having an ATREF temperature of T _x , which can be calculated from LnPxo = 0C / T _X o + β.

[078] Once the block index (BI) is obtained for each fraction of preparative TREF, the weight average block index, ABI, for the whole polymer can be calculated. In some embodiments, ABI will be greater than zero, but less than about 0.3, or from about 0.1 to about 0.3. In some embodiments, ABI will be greater than about 0.3 and even about 1.0. Preferably, ABI should be in the range of about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, ABI will be about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about 0 , 3 to about 0.6, about 0.3 to about 0.5, or about

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0.3 to about 0.4. In some embodiments, ABI will be in the range of about 0.4 to about 1.0, about 0.5 to about 1.0, about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

[079] Another characteristic of the ethylene / a-olefin interpolymer is that the ethylene / a-olefin interpolymer comprises at least a fraction of polymer that can be obtained by TREF, with the fraction having a block index greater than about from 0.1 to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3. In some embodiments, the polymer fraction will have a block index greater than about 0.6 and up to about 1.0, greater than about 0.7 to about 1.0, greater than about 0.8 to up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction will have a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction will have a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0, 3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. In still other embodiments, the polymer fraction will have a block index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0, 4 and up to about 0.7, or greater about 0.5 and up to about 0.6.

[080] For copolymers of ethylene and an α-olefin, the inventive polymers preferably have (1) a PDI of

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33/126 at least 1.3, more preferably at least 1.5, more preferably at least 1.7, or at least 2.0, and most preferably at least 2.6, up to a maximum of 5.0 , more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; (2) a heat of fusion of 80 J / g or less; (3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, T _g , of less than -25 ° C, more preferably less than about -30 ° C, and / or (5) only one T _m .

[081] Furthermore, the inventive polymers may have, alone or in combination with other properties disclosed here, a storage module, G ', such that the log (G') is greater than or equal to 400 kPa, preferably greater than or equal at 1.0 MPa, at a temperature of 100 ° C. Furthermore, the inventive polymers have a relatively flat storage module as a function of the temperature in a range of 0 to 100 ° C (illustrated in figure 6) that is characteristic of block copolymers, and previously unknown for an olefin copolymer, especially an ethylene copolymer and one or more C38 aliphatic α-olefins. (By the relatively flat term in this context it means that the log of G '(in Pascals) decreases by less than an order of magnitude between 50 and 100 ° C, preferably between 0 and 100 ° C).

[082] The inventive interpolymers may additionally be characterized by a penetration depth by thermomechanical analysis of 1 mm at a temperature of at least 90 ° C as well as a flexural modulus of about 20 MPa (3 kpsi) to 90 MPa (13 kpsi) ). Alternatively, inventive interpolymers may have

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34/126 a penetration depth by thermomechanical analysis of 1 mm at a temperature of 104 ° C as well as a flexural modulus of at least 20 MPa (3 kpsi). They can be characterized by having an abrasion resistance (or loss of volume) of less than 90 mm ³ . Figure 7 shows the TMA (1 mm) against the flexural module for the inventive polymers compared to other known polymers. The inventive polymers have a balance of flexibility and thermal resistance significantly better than other polymers.

[083] Additionally, ethylene / aolefin interpolymers may have a melt index,

I ₂ , from 0.01 to 2000 g / 10 minutes, preferably from

0, 01 to

1000 g / 10 minutes, more preferably from 0.01 to 500 g / 10 minutes, and especially from

0.01 to 100 g / 10 minutes. In certain embodiments, ethylene / a-olefin interpolymers have a melt index,

I ₂ , of

0.01 to g / 10 minutes, from 0.5 to g / 10 minutes, from 1 g / 10 minutes, from 1 to 6 g / 10 minutes, or from

0.3 g / 10 minutes.

In certain embodiments, the melt index for ethylene / a-olefin polymers of 1 g / 10 minutes, 3 g / 10 minutes or 5 g / 10 minutes [084]

The polymers may have molecular weights, M _w , of

1,000 g / mol to 5,000,000 g / mol, preferably 1000 g / mol to 1,000,000 g / mol, more preferably 10,000 g / mol to

500,000 g / mol, and especially 10,000 g / mol to g / mol. The density of inventive polymers may

300,000 be from

0.80 to 0.99 g / cm ³ and preferably for polymers comprising ethylene from 0.85 g / cm ³ to 0.97 g / cm ³ . In certain embodiments, the density of ethylene polymers / aPetition 870180058060, of 07/04/2018, p. 42/156

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olefin varies in 0.860 to 0.999 g / cm ³ or 0, 867 to 0.910 g / cm ³ . [085] 0 processes just to make the polymers was disclosed in the following patent applications: request in patent U.S provisional . n ° 60 / 553,906, deposited on 17 in March of 2004; request in provisional patent U.S. No. 60 / 662,937, deposited in 17 March 2005; request in patent U.S provisional . n ° 60 / 662,939, deposited on 17 in March of 2005; request in provisional patent U.S. No. 60 / 662,938,

filed on March 17, 2005; PCT patent application No. PCT / US2005 / 008916, filed on March 17, 2005; PCT patent application No. PCT / US2005 / 008915, filed on March 17, 2005; PCT patent application No. PCT / US2005 / 008917, filed on March 17, 2005, all of which are incorporated herein by reference. For example, such a method comprises contacting ethylene and optionally one or more addition-free polymerisable monomers of ethylene under conditions of addition polymerization with a catalyst composition comprising:

the reaction mixture or product obtained by combining:

(A) a first olefin polymerization catalyst having a high comonomer incorporation index, (B) a second olefin polymerization catalyst having a comonomer incorporation index less than 90 percent, preferably less than 50 percent, more preferably less than 5 percent of the comonomer incorporation index of the catalyst (A), and (C) a chain transfer agent.

[086] Representative chain transfer agents and catalysts are as follows.

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36/126 [087] Catalyst (Al) is [N- (2,6-di (1methylethyl) phenyl) starch) (2-isopropylphenyl) (a-naphthalen-2diyl (6-pyridin-2-diyl)] dimethyl hafnium , prepared in accordance with the teachings of WO 03/40195, 2003US0204017, US patent application serial number 10 / 429,024, filed on May 2, 2003, and WO 04/24740.

[088] Catalyst (A2) is [N- (2,6-di (1methylethyl) phenyl) starch) (2-methylphenyl) (1,2-phenylen-2-diyl (6pyridin-2-diyl) methane)] hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US0204017, US patent application serial number 10 / 429,024, filed on May 2, 2003, and WO 04/24740.

[089] Catalyst (A3) is bis [N, N '' -) 2,4,6tri (methylphenyl) starch) ethylenediamine] hafnium dibenzyl.

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[090] Catalyst (A4) is bis (2-oxoyl-3- (dibenzo-1Hpirrol-l-yl) -5- (methyl) phenyl) -2-phenoxymethyl) cyclohexane-1, 2-diyl zirconium (IV) dibenzyl, prepared substantially in accordance with the teachings of US-A-2004 0010103.

[091]

Catalyst

1,2-bis- (3,5-di-tbutylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl

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38/126 [092]

Catalyst / X —o, /

CH (CH ₃ ) ₂ (CH ₃ ) ₃

C (CH ₃ ) ₃ / CH (CH ₃ ) ₃ = N

M /

(B2)

C (CH ₃ ) jx = ch ₂ c ₆ h ₅

1,2-bis- (3,5-di-tbutylphenylene) (1- (N- (2-methylcyclohexyl) imino) methyl) (2-oxoyl)

Catalyst (Cl) is [093] (t-butylamido) dimethyl (3-Npirrolyl-1, 2,3, 3a, 7a-T | -inden-1-yl) dimethyl silanotitanium prepared substantially according to the techniques of the US patent No. 6,268,444.

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39/126 [094] Catalyst (C2) is di (4-methylphenyl (2-methyl-1, 2,3, 3a, 7a-T | -inden-1-yl) silanotitanium dimethyl (t-butylamido) prepared substantially in accordance with the teachings of the patent US-A-2003/004286 [095]

Catalyst (C3) is (t-butylamido) di (4-methylphenyl (2methyl-1, 2,3, 3a, 8a-T | -s-indacen-1-yl) silanotitanium dimethyl prepared substantially in accordance with the teachings of the patent US-A-2003/004286

bis (dimethyldisiloxane) (indene-1-yl) zirconium dichloride, commercially available from Sigma-Aldrich:

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Agents

transfer agents employed include diethylzinc, di (i-butyl) zinc, di (nhexyl) zinc, triethyl aluminum, trioctyl aluminum, triethyl aluminum, i-butyl aluminum bis (dimethyl (t-butyl) siloxane), i— butyl aluminum bis (di (trimethylsilyl)) amide), n-octyl aluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butyl aluminum, ibutyl aluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t- butylphenoxide, n-octyl aluminum di (ethyl) (1naphthyl) amide), ethyl aluminum bis (t-butyldimethylsiloxide), ethyl aluminum di (bis (trimethylsilyl) amide), ethyl aluminum bis (2,3,6,7-dibenzo-l-azacycloheptanoamide) , bis (2,3,6,7-dibenzo-1-azacycloheptanoamide), ethylaluminum n-octylaluminium bis (dimethyl (t-butyl) siloxide, ethylzinc (2,6-dipheniphenoxide), and ethylzinc (t-butoxide).

[098] Preferably, the above process takes the form of a continuous solution process to form block copolymers, especially multi-block copolymers, preferably linear multi-block copolymers of two or more monomers, more especially ethylene and a C ₄ -a-olefin. 2cu using multiple catalysts that are capable of

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41/126 interconversion. That is, the catalysts are chemically distinct. Under conditions of polymerization in continuous solution, the process is ideally suited for the polymerization of monomer mixtures according to high monomer conversions. Under these polymerization conditions, the transfer of the chain-transfer agent to the catalyst is favorable compared to chain growth, and multi-block copolymers, especially linear multi-block copolymers, are formed with high efficiency.

[099] The inventive interpolymers may be differentiated from random copolymers, physical mixtures of polymers, and conventional block copolymers, prepared by sequentially adding monomer, fluxional catalysts, anionic or cationic live polymerization techniques. In particular, compared to a random copolymer of the same monomers and the same monomer content at crystallinity or equivalent module, the inventive interpolymers have better (higher) thermal resistance, as measured by melting point, higher, higher TMA penetration temperature breaking load at high temperatures, and / or higher torsion storage module at high temperatures as determined by dynamic mechanical analysis. Compared to a random copolymer comprising the same monomers and monomer content, the inventive interpolymers have lower permanent compression strain, particularly at higher temperatures, lower stress relaxation, higher creep strain resistance, higher tear strength, greater blocking resistance, faster formation due to

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42/126 higher crystallization (solidification), higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better acceptance of oils and fillers.

[100] The inventive interpolymers also exhibit a unique relationship of crystallization and branching distribution. That is, the inventive interpolymers show a relatively large difference between the highest peak temperature measured using CRYSTAF and DSC as a function of the heat of fusion, especially compared to random copolymers comprising the same monomers and monomer levels or physical mixtures of polymers, such as as a mixture of a high density polymer and a lower density copolymer, at an equivalent overall density. It is believed that this unique characteristic of the inventive interpolymers is due to the unique distribution of the comonomer in blocks within the main polymeric chain. In particular, inventive interpolymers may comprise alternating blocks with different comonomer contents (including homopolymer blocks). The inventive interpolymers may also comprise a distribution in number and / or size of blocks of different density or comonomer content, which is a Schultz-Flory type distribution. In addition, the inventive interpolymers also have a single peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and morphology. In a preferred embodiment, the microcrystalline order of the polymers demonstrates spherulites and lamellae that are distinguishable from random block copolymers, even with PDI values that are less than

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1.7, or even less than 1.5, below even less than 1.3.

[101] Furthermore, inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. This is the amount of comonomer and length of each block or segment of polymer that can be changed by controlling the proportion and type of catalysts and transfer agent as well as the polymerization temperature, and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as the degree of block presence increases, the optical properties, tear resistance properties, and high temperature recovery of the resulting polymer are improved. In particular, the fog decreases, while the properties of clarity, tear resistance, and recovery at high temperatures increase as the average number of blocks in the polymer increases. By selecting combinations of transfer agents and catalysts having the desired chain transfer ability (high transfer rates with low levels of chain termination) other forms of polymer termination are effectively suppressed. Consequently, little or no β-hydride elimination is observed in the polymerization of ethylene / a-olefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, having little or no branching. long chain.

[102]

Polymers with highly crystalline chain terminations may be selectively prepared according to embodiments of the invention. In elastomer applications,

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44/126 reducing the relative amount of polymer that ends with an amorphous block reduces the intramolecular diluting effect in crystalline regions. This result can be obtained by choosing chain transfer agents and catalysts having the appropriate response to hydrogen or other chain terminators. Specifically, if the catalyst that produces highly crystalline polymers is more susceptible to chain terminations (such as by the use of hydrogen) than the catalyst responsible for producing the least crystalline polymer segment (such as through comonomer incorporation, regio-error, or higher atactic formation), then the highly crystalline polymer segments will preferably occupy the end portions of the polymer. The resulting terminating groups will not only be crystalline, but, upon termination, the highly crystalline polymer forming catalyst site will again be available for the re-initiation of polymer formation. Hence, the polymer initially formed will be another segment of highly crystalline polymer. Consequently, both ends of the multiblock copolymer are preferably highly crystalline.

[103] The ethylene / α-olefin interpolymers used in the embodiments of the invention will preferably be ethylene interpolymers with at least one C3C20 α-olefin · Ethylene copolymers and a C3-C20 α-olefin are especially preferred. The interpolymers may additionally comprise a C4-C18 diolefin and / or an alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or non-conjugated dienes

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45/126 conjugates, polyenes, alkenylbenzenes, etc. Examples of such comonomers include C3-C20 α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene , and the like. 1-Butene and 1-octene are especially preferred. Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics (e.g., cyclopentene, cyclohexene and cycloocene).

[104] While ethylene-a-olefin interpolymers are preferred polymers, other ethylene / olefin polymers may also be used. Olefins, as used here, refer to a family of compounds based on unsaturated hydrocarbons with at least one carbon-carbon bond. Depending on the selection of catalysts, any olefin can be used in embodiments of the invention. Preferably, suitable olefins are composed

C3-C20 aliphatics or aromatics comprising vinyl unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene, and norbornene, including, but not limited to, norbornene substituted in position 5 or 6 with hydrocarbyl or C1-C20 cyclohydrocarbyl groups · Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.

[105] Examples of olefin monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, and 1dodecene, eicosene,

1-tetradecene, 1-hexadecene, 1-octadecene, 13-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,

4,6-dimethyl-l-heptene,

4-vinylcyclohexene,

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46/126 vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C ₄ -C ₄ o dienes, including, but not limited to, 1,3-butadiene,

1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C ₄ -C ₄ o α-olefins, and the like. In certain embodiments, α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. Although any vinyl-containing hydrocarbon group could potentially be used in embodiments of the invention, practicalities such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become problematic as the molecular weight of the monomer becomes too high.

[106] The polymerization processes described here are well suited for the production of olefin polymers comprising aromatic monovinylidene monomers, including styrene, o-methyl styrene, p-methyl styrene, butyl styrene, and the like. In particular, interpolymers comprising ethylene and styrene can be prepared following the teachings here. Optionally, copolymers comprising ethylene, styrene and a C ₃ -C ₂ o alpha-olefin may be prepared, optionally containing a C ₄ -C ₂ o diene having improved properties.

[107] Suitable unconjugated diene monomers may be a straight chain, branched, or cyclic hydrocarbon diene having 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, acyclic straight chain dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9

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47/126 decadiene, branched-chain acyclic dienes, such as

5-methyl-1,4-hexadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyricene, and dihydrookinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene,

1.4- cyclohexadiene, 1,5-cyclooctadiene, and 1,5cyclododecadiene; and fused or bridged multiple ring alicyclic dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-

2.5- diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2norbornene (MNB); 5-cyclohexylidene-2-norbornene, 5-propenyl2-norbornene, 5-isopropylidene-2-norbornene, 5— (4 - cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene,

5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2 norbornene (MNB), and dicyclopentadiene (DCPD). Especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and

1,4-hexadiene (HD).

[108] A class of desirable polymers that can be made according to embodiments of the invention are elastomeric interpolymers of ethylene, a C ₃ C ₂ α-olefin, especially propylene, and optionally one or more diene monomers. α-Olefins preferred for use in this embodiment of the present invention are designated by the formula CH ₂ = CHR *, where R * is a linear or branched alkyl group with 1 to 12 carbon atoms. Examples of suitable aolefins include, but are not limited to, propylene, isobutylene, 1-butene,

1-pentene,

1-hexene,

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48/126 methyl-1-pentene, and 1-octene. A particularly preferred α-olefin is propylene. Propylene-based polymers are generally referred to as EP or EPDM polymers. Dienes suitable for use in the preparation of such polymers, especially multiblock EPDM-type polymers, include cyclic or polycyclic dienes, straight or branched chain, conjugated or unconjugated, comprising from 4 to 20 carbon atoms. Preferred dienes include 1,4 pentadiene, 1,4 hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene.

[109] Since polymers containing diene comprise alternating segments or blocks containing greater or lesser amounts of diene (including none) and α-olefin (including none), the total amount of diene and α-olefin can be reduced without loss of subsequent properties of the polymer. That is, since the diene and aolefin monomers are preferably incorporated into a type of polymer block rather than uniformly or randomly throughout the polymer, they are more efficiently used and subsequently the crosslink density of the polymer can be better controlled . Such crosslinkable elastomers and cured products have advantageous properties, including higher breaking load and better elastic recovery.

[110] In some embodiments, the inventive interpolymers made with two catalysts incorporating different amounts of comonomer have a weight ratio of blocks thus formed from 95: 5 to 5:95. The polymers

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49/126 elastomers desirably have an ethylene content of 20 to 90 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 10 to 80 percent, based on the total weight of the polymer. Furthermore, preferably, multiblock elastomeric polymers have an ethylene content of 60 to 90 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 10 to 40 percent, based on in the total weight of the polymer. Preferred polymers are high molecular weight polymers, having a weight average molecular weight (M _w ) of 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000, and a polydispersity of less than 3.5 , more preferably less than 3.0, and a Mooney viscosity (ML (1 + 4) 125 ° C) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75 percent, a diene content 0 to 6 percent, and an α-olefin content of 20 to 35 percent.

[111] Ethylene / α-olefin interpolymers may be functionalized by incorporating at least one functional group in their polymer structure. Exemplary functional groups may include, for example, ethylenically unsaturated mono- and difunctional carboxylic acids, anhydrides of ethylenically unsaturated monodi-functional carboxylic acids, salts thereof and esters thereof. Such functional groups may be grafted into an ethylene / α-olefin interpolymer, or they may be copolymerized and an optional additional comonomer to form an ethylene interpolymer, the functional comonomer and, optionally, other comonomer (s). Means for grafting functional groups in the polyethylene are described for example in U.S. Patent ^Nos

4,762,890, 4,927,888, and 4,950,541, the disclosures of these

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50/126 patents being fully incorporated by reference. A particularly useful functional group is malic anhydride.

[112] The amount of functional group present in the functional interpolymer may vary. Typically, the functional group may be present in a functionalized copolymer-type interpolymer in an amount of at least about 1.0 weight percent, at least about 5 weight percent, and more preferably at least about 7 percent in weight. The functional group will typically be present in a copolymer-like functionalized interpolymer in an amount of less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.

[113] The amount of ethylene / a-olefin interpolymer in the polymer composition disclosed here may be as much or as little to achieve the desired properties. For example, typical applications may require about 5% w / w to about 95% w / w, about 10% w / w to about 95% w / w, about 20% w / w to about 95 % w / w, about 30% w / w about 95% w / w, about 40% w / w about 95% w / w, about 50% w / w about 95% w / w, or about 60% w / w about 95% w / w of the total weight of the composition. In some embodiments, the amount of ethylene / α-olefin interpolymer in the polymer composition is about 70% w / w to about 75% w / w, based on the total weight of the polymer composition.

Polypropylene [114] Polymer compositions comprise at least one polypropylene that can improve or modify

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51/126 properties, for example, melt strength, of polymer compositions. Any polypropylene known to those of ordinary skill in the subject may be used to prepare the compositions disclosed here. Non-limiting examples of polypropylenes include random polypropylenes, including low density polypropylene (PPBD), high density polypropylene (PPAD), high melt strength polypropylene (PP-ARF), high impact polypropylene (PPAI), isotactic propylene (PPi ), syndiotatic polypropylene (PPs) and the like, and combinations thereof. In some embodiments, polypropylene is a polypropylene with relatively high melt strength. In other embodiments, the polypropylene is a branched polypropylene.

[115] In additional embodiments, polypropylene has a melt flow rate of, I ₂ , from about 0.01 to about 2000 g / 10 min., From about 0.01 to about 1000 g / 10 min., from about 0.01 to about 500 g / 10 min., or from about 0.01 to about 100 g / 10 min., measured with a load of 2.16 kg at 230 ° C, according to ASTM 1238. In certain embodiments, polypropylene has a melt flow rate from about 1 to about 100 g / 10 minutes, from about 2 to about 75 g / 10 minutes, from about 3 to about 50 g / 10 minutes, measured with a load of 2.16 kg at 230 ° C according to ASTM D 1238. In other embodiments, the melt flow rate, I ₂ , for polypropylene, is at least about 0.5 g / 10 min., at least about 1 g / 10 min., at least about 3 g / 10 min., at least about 5 g / 10 min., at least about 7, 5 g / 10 min., At least about 10 g / 10 min, at least about 15 g / 10 min., Or at least 20

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52/126 g / 10 min., Measured with a load of 2.16 kg at 230 ° C, according to ASTM 1238.

[116] In additional embodiments, branched polypropylenes often have a delta tg value at 0.1 radian per second of less than about 2.5, preferably less than about 1.5, more preferably less than about 1, 0. As one skilled in the art will appreciate, the delta tg generally refers to the elasticity of a material and is the ratio of the loss module to the storage module. Generally, the larger the storage module, the lower the delta tg and the more elastic the material. Evidently, that more elasticity may be related to higher molecular weight and greater branching. Delta tg measurements are generally made using a Rheometric Scientific Advanced Rheomterics Expansion System (ARES) instrument having a 25 mm diam. Parallel plates with approx. 0.002 inch in shear mode of the oscillator with the plates parallel to a 15% deformation, a 2000 gram transducer and a nitrogen purge. Measurements are taken at 5 points per decade from 0.1 to 100 radians per second at 190 ° C. Further details are found below entitled DMA. Some examples of ARF polypropylenes or branched polypropylenes include PROFAX® PF 814, commercially available from Basell Polyolefins, Elkton, MD; INSPIRE® HMS from The Dow Chemical Company, Midland, MI; and Borealis DAPLOY® WB260HMS, Kongens Lyngby, Denmark. Some ARF polypropylenes or branched polypropylenes can be obtained by known methods, such as those described by D. Graebling, Synthesis of Branched Polypropylene by a Reactive Extrusion

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53/126

Process, Macromolecules, 35 (12), 4602 = 4610 (2002); Langston et al., One-pot process of preparing long chain branched polypropylene using C [2] -symmetric metallocene complex and a T reagent, Macromolecules, 38 (14), 5849-5853, (2005); and US Patent ^Nos 6,599,985 and 6,875,826, all of which being incorporated herein by reference.

[117] The amount of polypropylene in the polymer composition varies by application. Typically, the amount can be from about 5% w / w to about 95% w / w. In some embodiments, the amount of polypropylene in the polymer composition is about 10% w / w, about 90% w / w, about 15% w / w, about 85% w / w, about 20% w / w about 75% w / w or 25% w / w about 70% w / w, based on the total weight of the polymer composition. In other embodiments, the polymer composition comprises the ethylene / a-olefin interpolymer and polypropylene in a ratio of about 10: 1, about 5: 1, about 3: 1, about 1: 1, about 1: 3, about 1: 5 or about 1:10 by weight. In additional embodiments, the amount of polypropylene in the polymer composition is about 10% w / w, about 20% w / w, about 25% w / w, about 30% w / w, about 40% w / w, or about 50% w / w, based on the total weight of the polymer composition. In certain embodiments, the amount of polypropylene in the polymer composition is about 20% w / w to about 25% w / w, based on the total weight of the polymer composition.

Additives [118] Optionally, the polymer compositions disclosed herein may comprise at least one additive composition for the purpose of improving and / or controlling properties

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54/126 processability, appearance, chemical and / or mechanical, of polymer compositions. Additives for conventional plastics known to those of ordinary skill in the art may be useful in the polymer compositions disclosed here. Non-limiting examples of additives suitable for additive composition include release agents, polysiloxanes, glidants, plasticizers, oils, antioxidants, UV stabilizers, colorants and pigments, fillers, lubricants, anti-fog agents, flow aids, coupling agents, crosslinking agents, nucleating agents, surfactants, solvents, flame retardants, antistatic agents, antimicrobials, agents against scratches and damages, and combinations thereof. In some embodiments, the polymer compositions will not comprise a poilisiloxane, a glidant, a plasticizer, an oil, an antioxidant, a UV stabilizer, a cross-linking agent, a nucleating agent, a surfactant, a solvent, a flame retardant , an antistatic agent, an antimicrobial agent, a scratch and damage agent, or a combination of two or more of the additives. In additional embodiments, the polymer compositions will not comprise any additives.

[119] amount of additive depends on the polymers employed, the desired applications, and the type of additive.

Typically when additives are employed, the total amount of the additives can vary from more than 0% w / w to about 50% w / w, from about 0.001% w / w to about 40% w / w, from

0.01% w / w at about

30% w / w, from about 0.1% w / w to about

20% w / w, of about

0.5% w / w to about 10% w / w or from about 1% w / w to about 5% w / w, based on the total weight of the

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55/126 polymer composition. Some polymer additives have been described in Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001) reference.

which is here fully incorporated by [120]

Optionally, the polymer compositions disclosed herein comprise at least one polysiloxane additive. Any polysiloxane that (1) can provide processing improvements such as better mold filling, less extruder torque, internal lubrication, demoulding, and faster processing, and / or (2) can modify surface characteristics, such as greater lubricity, less sliding, lower coefficient of friction, and greater resistance to scratches and damage can be used. In some embodiments, the polysiloxane is or comprises a high molecular weight polysiloxane. In additional embodiments, the polysiloxane is or comprises an ultra high molecular weight polydylalkylsiloxane. Some non-limiting examples of suitable polydialkylsiloxanes include polydylalkylsiloxanes having a C1-4 alkyl group, such as polydylethylsiloxanes, polydiethylsiloxanes, polymethylethylsiloxanes, polydipropylsiloxanes, and polydibutylsiloxanes. In certain embodiments, the polysiloxane additive is or comprises a mixture of an ultra high molecular weight polydialalkylsiloxane and a polyolefin, such as polyethylene, polypropylene or a combination thereof. Some non-limiting examples of such polysiloxane mixtures include standard DOW CORNING® MB50 series batches, such as DOW CORNING® MB50-001, MB50-002,

MB50-313, MB50-314, and MB50-321, all of which are commercially

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56/126 available from Dow Corning Corporation, Midland. MI.

[121]

In other embodiments, the polysiloxane is or comprises a liquid polysiloxane.

Some non-limiting examples of liquid polysiloxanes include low molecular weight polydylalkylsiloxanes, low molecular weight polyalkylphenylsiloxanes, and modified siloxane oils, such as olefin modified siloxane oils, polyether modified silicone oils, olefin / polyether modified silicone oils , epoxy-modified silicone oils, and alcohol-modified silicone oils.

[122] In some embodiments, the polysiloxane additive is or comprises a polydialkylsiloxane having a viscosity of about 100,000 to about 1,000,000. In additional embodiments, the polysiloxane additive is or comprises a polydialkylsiloxane having a viscosity of 1,000,000 to 10,000,000 centistokes. In certain embodiments, the polysiloxane additive is or comprises a polydialkylsiloxane having a viscosity of about 10,000,000 to about 50,000,000 of synthesis.

[123] When used, the amount of polysiloxane additive in the polymer composition may be from about 0.1% w / w to about 5.0% w / w, based on the total weight of the polymer composition.

In other embodiments, the amount of polysiloxane additive in the polymer composition is about

0.15% w / w to about 0.4% w / w, based on the total weight of the polymer composition.

In some embodiments, the polymer compositions do not comprise a polysiloxane.

[124] In some embodiments, the compositions of

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57/126 polymers disclosed here optionally comprise a colorant or pigment that may change the appearance of polymer compositions to human eyes. Any colorant or pigment known to the person with a moderate understanding of the subject may be added to the polymer compositions disclosed here. Non-limiting examples of dyes or pigments include pigments such as metallic oxides, such as organic oxides, such as iron, zinc oxide, and titanium dioxide, mixed metal oxides, smoke black, organic pigments, such as anthraquinones, anthranthones, azo and monoazo compounds, arylamides, benzimidazolones, BONA dicetopyrrole lakes pyrroles, dioxazins, diazo compounds, diarylide compounds, flavantrones, indantrones, isoindolinones, isoindolines, metal complexes, monoazo salts, naphthols, β-naphthols, naphthol, naphthol, naphthol, , perilenes, perinones, phthalocyanines, pyrantrones, quinacridones, and quinophthalones, and combinations thereof. When used, the amount of dye or pigment in the polymer composition may be from about 0 to about 10% w / w, from about 0.1 to about 5% w / w, from about 0, 25 to about 3% w / w, based on the total weight of the polymer composition. In some embodiments, the polymer compositions do not comprise a dye or pigment. Some colorants and / or pigments typical been described in Zweifel Hans et al, Plastics and Additives Handbook, Hanser Gardner Pulbications, Ciincinnati, Ohio, 5 ^to -. Edition, Chapter 15, pages 813-882, which is incorporated herein by reference.

[125] Optionally, the polymer compositions disclosed herein may comprise a plasticizer. In

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58/126 Overall, the plasticizer is a chemical compound that can increase flexibility and lower the glass transition temperature of polymers. Any plasticizer known to those of ordinary skill in the subject may be added to the polymer compositions disclosed here. Non-limiting examples of plasticizers include paraffinic oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers, and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates , phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromelitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers, hydroxybenzoic acid esters, isocyanate adducts, aromatic multi-ring compounds, derivatives of multiple rings natural, nitriles, siloxane-based plasticizers, tar-based products, and combinations of these. When used, the amount of plasticizer in the polymer composition may be greater than 0 to about 15% w / w, from about 0.5 to about 10% w / w, from about 1 to about 5% w / w of the total weight of the polymer composition. Some plasticizers have been described in George Wypych, Handbook of Plasticizers, Chem-Tec Publishing, Toronto-Scarborough, Ontario (2004), which is incorporated herein by reference.

[126]

In some embodiments, the polymer compositions disclosed here optionally comprise an antioxidant that may prevent oxidation of the polymer components and organic additives in the polymer compositions.

Any antioxidant known to that medium

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59/126 understood in the subject may be added to the polymer compositions disclosed here. Non-limiting examples of suitable antioxidants include aromatic or hindered amines such as diphenylamines, phenyl-a-naphthylamine, alkyl or aralkyl-substituted phenyl-a-naphthylamine, alkylated pphenyl diamines, tetramethyl-diaminodiphenylamine and the like; phenols, such as 2,6-di-t-butyl-4methylphenol,

1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4' hydroxybenzyl) benzene; tetrakis [(methylene (3,5-di-t-butyl-4-hydroxyhydrocinamate) methane (eg, IRGANOX ^mr 1010, from CibaGeigy, New York); phenols modified with acroyl; octadecyl3,5-di-t-butyl- 4-hydroxycinnamate (eg, IRGANOX ^mr 107 6, commercially available from Ciba-Geigy); phosphites, phosphonites;

hydroxylamines; benzofuranone derivatives;

combinations of these. When used, the amount of the antioxidant in the polymer composition may be from about greater than about 5% w / w, from about 0.0001 to about

2.5% w / w, from about 0.001 to about 1% w / w or about

0.001 to about 0.5% w / w.

based on the total weight of the polymer composition.

In some embodiments, the polymer compositions do not comprise an antioxidant.

Some antioxidants have been described in Zweifel

Hans et al.,

Plastics Additives Handbook,

Hanser Gardner

Publications,

Cincinnati, Ohio, 5th Edition,

Chapter 1, pages 1-140 (2001), which is incorporated by reference.

[127] In other embodiments, the polymer compositions disclosed here optionally comprise a UV stabilizer that can prevent or reduce the degradation of polymer compositions by UV radiation. Any UV stabilizer known to that medium understood

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60/126 on the subject may be added to the polymer compositions disclosed here. Non-limiting examples of suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metal salts, zinc compounds and combinations of these. When used, the amount of UV stabilizer in the polymer composition may be greater than 0 to about 5% w / w, from 0.01 to about 3% w / w. from about 0.1 to about 2% w / w, or from about 0.1 to about 1% w / w of the total weight of the polymer composition. In some embodiments, the polymer compositions do not comprise a UV stabilizer. Some UV stabilizers have been described in Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, lines 141-426 (2001), which is incorporated herein by reference.

[128] Optionally, the polymer compositions disclosed here may comprise a filler that can be used to adjust, among others, volume, weight, costs, and / or technical performance. Any charge known to those of ordinary skill in the matter may be added to the polymer compositions disclosed here. Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina, such as hydrated alumina, glass microspheres, ceramic microspheres, thermoplastic microspheres, marble powder, cement powder, magnesium oxide, hydroxide

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61/126 magnesium, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, fiberglass, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, fiberglass, or a mixture thereof. When used, the amount of filler in the polymer composition can be from about 0 to about 80% w / w. from about 0.1 to about 60% w / w. from about 0.5 to about 40% w / w, from about 1 w / w to about 30% w / w, or from about 10 to about 40% w / w of the total weight polymer composition. In some embodiments, the polymer compositions do not comprise a charge. Some fillers have been disclosed in US Patent No. 6,103,803 and Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, lines 901-948 (2001), is incorporated herein by reference.

[129] Optionally, the polymer compositions may comprise a lubricant. In general, the lubricant can be used, among others, to modify the rheology of molten polymer compositions, to improve the surface finish of molded articles, and / or to facilitate the dispersion of fillers or pigments. Any lubricant known to one of ordinary skill in the matter may be added to the polymer compositions disclosed here. Non-limiting examples of lubricants include fatty alcohols and their esters of dicarboxylic acids, fatty acid esters of short-chain alcohols, fatty acids,

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62/126 fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of long chain alcohols, lignite waxes, polyethylene waxes, polypropylene waxes, natural or synthetic paraffin waxes, fluoropolymers and combinations of these .

amount of lubricant in the composition

When used, that of polymer may be more than up to about 5% w / w, from about 0.1 to about 4% w / w, from about 0.1 to about 3% w / w p of the total weight of the polymer composition.

In some embodiments, the polymer compositions do not comprise a lubricant. Some suitable lubricants have been disclosed in Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, lines 511-552 (2001), which is incorporated herein by reference.

[130] Optionally, the polymer compositions disclosed herein may comprise an antistatic agent. Generally, the antistatic agent can increase the conductivity of the polymer compositions and prevents the accumulation of static charge. Any antistatic agent known to those of ordinary skill in the subject may be added to the polymer compositions disclosed here. Non-limiting examples of antistatic agents include conductive fillers (eg, carbon black, metallic particles, and other conductive particles) fatty acid esters (eg, glycerol monostearate), ethoxylated alkylamines, diethanolamides, alcohols ethoxylates, alkyl sulfonates, alkyl phosphates, quaternary ammonium salts, alkyl betaines, and combinations thereof. When used, the amount of antistatic agent in the polymer composition

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63/126 may be about greater than 0 to about 5% w / w, about 0.01 to about 3%, or about 0.1 to about 2% w / w of the total weight of the polymer composition. Some suitable antistatic agents have been disclosed in Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10, lines 627-646 (2001), which is incorporated herein by reference.

[131] In additional embodiments, the polymer compositions disclosed here optionally contain a crosslinking agent that can be used to increase the crosslink density of the polymer compositions. As used herein, cross-linking agent means any means that cross-links polymer compositions. Therefore, crosslinking agents may be chemical compounds, but they are not necessarily so. Non-limiting examples of crosslinking agents as used here also include electron beam radiation, beta irradiation, gamma irradiation, corona irradiation, allyl compounds and UV radiation with or without organic peroxides, crosslinking catalysts eg, alkyl peroxides, peroxides allyl, peroxyesters, peroxycarbonates, diacyl peroxides, peroxycetals and cyclic peroxides) and silanes (eg, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxylsilane, vinylmethyldimethoxyethylsilane, and 3-methoxyethylsilane. The US patent No 6,803,014 and 6,667,351 disclose ^the irradiation with electron beam methods that can be used in embodiments of the invention. When used, the amount of a compound as a crosslinking agent can be from about greater than 0 to

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64/126 about 20% w / w, about 0.1 to about 15% w / w, or about 1 to about 10% w / w of the total weight of the polymer composition. In some embodiments, the compositions do not comprise a crosslinking agent. Some suitable cross-linking agents have been disclosed in Zweifel Hans et al., Plastics and Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, lines 725-812 (2001), which is incorporated herein by reference.

[132] In additional embodiments, the polymer compositions disclosed herein optionally comprise a coagent or coupling agent. Such coagents or coupling agents may be used with the crosslinking agents mentioned above. Any suitable coagent or coupling agent known to one of ordinary skill in the art can be added to the polymer compositions described herein. Non-limiting examples of suitable agents include those based on acrylate compounds, allyl compounds, etc.

Preparation of the Polymer Compositions [133] The ingredients of the polymer compositions, i.e., the ethylene / a-olefin interpolymer, polypropylene, and optional additives, may be mixed or mixed using methods known to that of ordinary skill in the subject, preferably methods that provide a substantially homogeneous distribution of the polypropylene and / or the additives in the ethylene / α-olefin interpolymer. Non-limiting examples of mixing methods include dry mixing, melt mixing, solvent mixing, extrusion, and the like.

[134] In some embodiments, monitoring devices

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65/126 physical mixing that provides dispersive mixing, distributive mixing or a combination of dispersive and distributive mixtures may be used. Non-limiting examples of batch methods include those using BRABENDER® mixing equipment (eg, BRABENDER PREP CENTER®, commercially available from W. Brabender Instruments, Inc., South Hackensack, NJ) or internal mixing and mixing equipment with BANBURY® rollers (commercially available from Farrel Company, Ansonia, Conn.). Non-limiting examples of continuous methods include single-screw extrusion, double-screw extrusion, alternating single-screw extrusion, and single-screw extrusion and pin cylinder (pin barrei). In some embodiments, additives may be added to the extruder via a hopper or feed hopper during the extrusion of the ethylene / a-olefin interpolymer, polyolefin or polymer composition. Mixing or blending of polymers by extrusion has been described in C. Rauwendaal, Polymer Extrusion, Hanser Publishers, New York, NY, pages 322-334, which is incorporated herein by reference.

Applications of polymer compositions [135] The polymer compositions disclosed here can be used to manufacture plastic plates or sheets or rolls that can be used to prepare various thermoformed articles for the automotive, construction, medical, food and beverage, electrical markets , home appliances, office machines, and consumer goods. In some embodiments, the plates comprising the polymer compositions are thermoformed into articles of

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66/126 interior such as decorative panels or skins providing superficial aesthetics, without paint to cars or other transport vehicles. In other embodiments, the sheets comprising the polymer compositions are thermoformed into exterior articles, such as bumper panels, stirrups, hoods, roof panels, truck and trailer panels, such as claws, and extreme covers for automobiles and vehicles utilities. In additional embodiments, the plates comprising the polymer compositions are used to replace steel, aluminum, glass-reinforced composites, and plastics in various applications for the automotive, construction, medical, food and beverage, electrical, appliance, office machines, and consumer machines.

[136] Polymer compositions may be made into sheets or sheets or rolls by known polymer processes, such as extrusion (eg, sheet extrusion and profile extrusion), injection molding, injection overmolding, molding, and rotational molding. In general, extrusion is a process by which a polymer is propelled continuously along a thread through regions of high temperature and pressure where it is melted and compacted, and finally forced through a matrix. The extruder may be a single screw extruder, a multiple screw extruder, a disk extruder, or a plunger extruder. Extrusion polymers have been described by C. Rauwendaal, Polymer Extrusion, Hanser Publishers, New York, NY (1986); and M.J.Stevens, Extruder Principal and Operation, Ellsevier Applied Science Publishers, New York, NY (1985), both of which are here in full

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67/126 incorporated by reference.

[137] Molding is generally a process by which a polymer is melted and conducted into a mold, which is the inverse of the desired shape, to form parts of the desired shape and size. The impression can be assisted by pressure or without pressure. Polymer molding is described in Hans-Georg Elias An Introduction to Plastics, Wiley-VCH, Weinhei, Germany, pages 161-163 (2003), which is incorporated herein by reference.

[138] Rotational molding is a process generally used to produce hollow plastic products. Using additional post-molding operations, complex components can be produced as effectively as by other molding and extrusion techniques. Rotational molding differs from other processing methods in that the stages of heating, melting, forming and cooling all occur after the polymer is placed in the mold, hence no external pressure is applied during forming. Rotational polymer molding has been described in Glenn Beall, Rotational Molding: Design, Materials & Processing, Hanser Gardner Publications, Cincinnati, Ohio (1998), which is incorporated herein in its entirety by reference.

[139] In some embodiments, the polymer compositions are extruded into plates, sheets or rolls which can subsequently be used to prepare various articles by thermoforming or other plastic processes known to those skilled in the art. The extruded plates or sheets or rolls may have a single layer or multilayer construction. Generally, extruded plates, sheets or rolls may have a

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68/126 thickness from about 0.354 mm to about

2.54 cm (0.01 inch to 1.0 inch), about 1.27 mm to about 1.91 cm (0.05 inch to about 0.75 inch), or about

2.54 cm to about 1.27 cm (0.01 inch to

0.5 inch).

[140]

The extruded plates, sheets or rolls in general can be used to make various articles thermoformed by the thermoforming process. Thermoforming is the pressing or compression of a flexible material, such as thermoplastic plates, to the final shape. The flexible material can be heated by infrared, natural gas, or other heaters or stoves to its formation temperature. Then, it can be stretched over or into a temperature controlled, single surface mold.

The molds can be engraved with patterns ranging from coarse fines, to simulate an artificial or natural or granular appearance.

The flexible material is retained against the surface unit of the mold until it cools.

The formed part is then trimmed from the flexible material.

There are several categories of thermoforming, including vacuumforming, pressure forming, double sheet forming, single forming.

in curtain books, free blowing, and sheet folding

Various thermoforming processes are disclosed such as L. Throne, Understanding Thermoforming,

Hanser Gardner Publications, Inc., Cincinnati, OH, 1999; and

J.L. Throne Technology of Thermmoforming, Hanser Verlag, Munich, 1996, both of which are incorporated herein by reference.

[141] Forming processes other than conventional thermoforming processes are also suitable for the manufacture of articles from the polymer compositions disclosed here. They include variations, such as pre-softening the sheet

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69/126 extruded to temperatures below the final melting temperature, cutting smooth regions (ie, whites) of the sheet, transferring the whites by gravity or mechanical means into married molds whereby whites are conformed to the article by heat and pressure . Conventional cardboard pressing equipment and corresponding forming tools are optionally modified to produce articles of this invention.

[142] The thermoforming process may be carried out at a temperature higher than the softening temperature of the polymer compositions disclosed here. In some embodiments, the thermoforming temperature is from about 80 ° C to about 300 ° C, from about 100 ° C to about 280 ° C, from about 140 ° C to about 240 ° C. In other embodiments, the thermoforming temperature is about 160 ° C to about 220 ° C.

[143] In some embodiments, the polymer compositions disclosed herein may be used to make films or hollow articles such as plastic containers by means of blow molding. The process includes positioning a softened polymer in the center of a mold, inflating the polymer against the walls of the mold with a blow pin, and solidifying the product by cooling. There are three general types of blow molding: extrusion blow molding, injection blow molding, and stretch blow molding. Injection blow molding can be used to process polymers that cannot be extruded.

[144] Stretch blow molding can be used for crystalline difficult to blow polymers and

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70/126 crystallizable, such as polypropylene. Polymer blow molding has been described by Norman C. Lee, Understanding Blow Molding, Hanser Gardner Publications, Cincinnati, Ohio (2000), which is incorporated herein by reference.

[145] The following examples are presented to exemplify embodiments of the invention. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details described in each example should not be understood as characteristics necessary for the invention.

EXAMPLES

Test Methods [146] In the following examples, the following analytical techniques are employed:

[147] GPC method for Samples 1-4 and AC [148] An automated liquid handling robot equipped with a set of needles heated to 160 ° C is used to add enough 1,2,4-trichlorobenzene stabilized with 300 ppm of Ionol for each polymer sample dried to give a final concentration of 30 mg / mL. A small glass stirring rod is placed in each tube and the samples are heated to 160 ° C for 2 hours on a heated orbital shaker by rotating

250 rpm.

concentrated polymer solution is then diluted to mg / mL using the automated liquid handling robot the set of heated needles to

160 ° C.

[149]

A GPC system

Symyx Rapid is used to

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71/126 determine the molecular weight data for each sample. A Gilson 350 pump set adjusted to a flow rate of 2.0 mL / min is used to pump 1,2-dichlorobenzene purged with helium stabilized with 300 ppm Ionol as the mobile phase through three 10 micron Plgel columns ( | lm) Mixed B 300 mm x 7.5 mm placed in series and heated to 160 ° C. A Polymer Labs ELS 1000 Detector is used with the Evaporator set at 250 ° C, the Nebulizer set at 165 ° C, and the nitrogen flow rate at 1.8 SLM at a pressure of 400-600 kPa (60- 80 psi) of N ₂ . The polymer samples are heated to 160 ° C and each sample is injected into a 250 gL loop using the liquid handling robot and a heated needle. A serial analysis of the polymer samples uses two switched loops and overlapping injections are used. Sample data is collected and analyzed. Sample data is collected and analyzed using the Symyx Epoch ^MR software. The peaks are manually integrated and the molecular weight information is reported uncorrected against a standard polyester calibration curve.

CRYSTAF Standard Method [150] Branch distributions are determined by Crystallization Fractionation Analysis (CRYSTAF) using a commercially available CRYSTAF 200 unit from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4-trichlorobenzene at 160 ° C (0.66 mg / ml) during stabilization at 95 ° C for 45 minutes. Sampling temperatures range from 95 to 30 ° C at a cooling rate of 0.2 ° C / min. An infrared detector is used to measure the concentrations of the polymer solution. The soluble concentration

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Cumulative 72/126 is measured as the polymer crystallizes while the temperature is reduced. The analytical derivative of the cumulative profile reflects the short chain branch distribution of the polymer.

[151] The CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF software (Version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak search routine identifies a peak temperature as a maximum in the dW / dT curve and the area between the largest positive inflections on each side of the peak identified in the derived curve. To calculate the CRYSTAF curve, the preferred processing parameters are with the limit temperature of 70 ° C and the extrapolation parameters above the limit temperature of 0.1, and below the limit temperature of 0.3.

Standard DSC Method (Excluding Samples 1-4 and A-C) [152] Differential Scanning Calorimetry results are determined using a DSI TAI model Q1000 equipped with an RCS cooling accessory and a self-sampler. A flow of nitrogen purge gas of 50 mL / min is used. The sample is pressed into a thin film and melted in the press at about 175 ° C and then cooled in air to room temperature (25 ° C). 3-10 mg of material are then cut into 6 mm diameter discs, precisely weighed, placed in a light aluminum pan (about 50 mg), then closed and seamed. The thermal behavior of the sample is investigated with the following temperature profile. The sample is quickly heated to 180 ° C and kept isothermal for 3 minutes to remove any previous thermal history. The sample is then

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73/126 cooled to -40 ° C at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. The sample is then heated to 15 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.

[153] The DSC melting peak is measured as the maximum in heat flow rate (W / g) with respect to the linear baseline drawn between -30 ° C and the end of the melt. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of fusion using a linear baseline.

GPC method (Excluding Samples 1-4 and A-C) [154] The gel permeation chromatographic system consists of either a Polymer Laboratories Model PL210 instrument or a Polymer Laboratories Model PL-220 instrument. The carousel column and compartments are operated at 140 ° C. Three 10-micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. The samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by gently shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 mL / minute.

[155] GPC column set calibration is performed with 21 polystyrene standards with narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 cocktail mixes with at least a decade of weight separation individual molecules. The standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared with 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and with

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0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures with narrow patterns are processed first and in order to reduce the component with the highest molecular weight to minimize degradation. The peak molecular weights of polystyrene standards are converted to molecular weights of polyethylene using the following equation (as described by Williams and Ward, J. Poly, Sei., Polym. Let., 6, 621 (1968): Mpoüetiieno 0/431 (Mpoüestireno) [156] Calculations of equivalent molecular weight of polyethylene are performed using the Viscotek TriSec Version 3.0 software.

Permanent Compression Deformation [157] Permanent compression deformation is measured according to ASTM D 395. The sample is prepared by stacking circular discs with a diameter of 25.4 mm, 3.2 mm, 2.0 mm, and 0.25 mm thick until a total thickness of 12.7 mm is achieved. The discs are cut from 12.7 cm x 12.7 cm plates molded by compression with a heated press under the following conditions: zero pressure for 3 min at 190 ° C, followed by 86 MPa for 2 min at 190 ° C , followed by cooling inside the press with cold running water at 86 MPa.

Density [158] Samples for density measurements are prepared according to ASTM D 1928. Measurements are made within one hour of pressing the sample using ASTM D792, Method B. Flexional / Drying Module / Storage Module [159] Samples are compression molded using ASTM D

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1928. Measurements are made within one hour difference pressing using ASTM D792, Method B.

Optical properties [160] 0.4 mm thick films are molded by compression using a heated press (Carver Model # 40954PR1001R). The pellets are placed between polytetrafluoroethylene sheets, heated to 190 ° C at 380 kPa (55 psi) for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min. The film is then cooled in the press with cold running water at 1.3 MPa for 1 min. Compression-molded films are used for optical measurements, tractive behavior, recovery, and stress relaxation.

[161] Clearness is measured using a BYK Gardner Haze-gard as specified in ASTM D 1746.

[162] 45 ° gloss is measured using a BYK Gardner Glossmeter Microgloss 45 ° as specified in ASTM D2457.

[163] Internal fog is measured using BYK Gardner Hazegard based on ASTM D 1003 Procedure A. Mineral oil is applied to the surface of the film to remove surface scratches.

Mechanical Properties - Tractive, Hysteresis, and Tear [164] The stress-strain behavior under uniaxial stress is measured using microtensile test bodies according to ASTM D 1708. The samples are stretched with an Instron up to 500% min ^-1 at 21 ° C. Tensile strength and elongation at break are reported as an average of 5 test bodies.

[165] 100% and 300% hysteresis is determined from cyclic loading at 100% and 300% strain using

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76/126 microtensile test bodies according to ASTM D 1708 with an Instron ^MR instrument. The sample is loaded and unloaded at 267% min ^-1 for 3 cycles at 21 ° C. Cyclic experiments at 300% and 80 ° C are conducted using an environmental chamber. In the 80 ° C experiment, the sample is left to equilibrate for 45 minutes at the test temperature before the test. In the cyclic experiment at 300% strain at 21 ° C, the refractive stress at 150% strain from the first discharge cycle is noted. The percentage of recovery for all experiments is calculated from the first unloading cycle using the strain in which the load has returned to the baseline. The recovery percentage is defined as:

£ f ~ £ s

Recovery% = ------- x 100 £ f where Cf is the strain taken from a cyclic loading and e _s is the strain when the load returns to the baseline during the first unloading cycle.

[166] Stress relaxation is measured at 50 percent strain and 37 ° C for 12 hours using an Instron ^MR instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C for 45 min in the environmental chamber, the sample was stretched to 50% 333% min ^-1 . The voltage was recorded as a function of the time to 12 hours. Percentage tension relaxation after 12 hours was calculated using the formula:

Lo ~ L12

Stress relaxation% = --------- x 100 £ f where L _o is the load at 50% strain in time 0 and L _i2 is the load at 50% stress after 12 hours.

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77/126 [167] Tractive notched tearing experiments are performed on samples having a density of 0.88 g / cm ³ or less using an Instron ^MR instrument. The geometry consists of a 76 mm x 13 mm x 0.4 mm gauge section with a 2 mm notch cut in the sample in half the length of the test body. The sample is stretched at 508 mm min ^-1 at 21 ° C until it breaks. The tear energy is calculated as the area under the stress-elongation curve until deformation at maximum load. An average of at least 3 test bodies is reported.

TMA [168] Thermal Mechanical Analysis (Penetration Temperature) is conducted on compression-molded discs 30 mm in diameter x 3.3 mm thick, formed at 180 ° C and molding pressure of 10 MPa for 5 minutes and then suddenly cooled in the air. The instrument used is a TMA 7, a commercially available brand from Perkin-Elmer. In the test, a probe with a 1.5 mm radius tip (PN N519-0416) is applied to the sample disc with a force of 1 N. The temperature is increased to 5 ° C / min from 25 ° C. The probe's penetration distance is measured as a function of temperature. The experiment ends when the probe has penetrated 1 mm in the sample.

DMA [169] Dynamic Mechanical Analysis (DMA) is measured on compression-shaped discs formed in a press heated to 180 ° C at a pressure of 10 MPa for 5 minutes and then cooled in the press at 90 ° C / min. The tests are conducted using an ARES controlled strain rheometer (TA Instruments) equipped with dual overhang adapters

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78/126 for torsion tests.

[170] A 1.5 mm plate is pressed and cut like a bar with dimensions of 32x12 mm. The sample is fixed at both ends by claws separated by 10 mm (claw separation (AL) and subjected to successive temperature steps from -100 ° C to 200 ° C (5 ° C per step). Torsion torque G 'is measured at an angular frequency of 10 rad / s, the strain range being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.

[171] An initial static force of 10 g is maintained (self-tensioning module) to prevent loosening of the sample when thermal expansion occurs. As a consequence, the separation of claws A1 increases with temperature, particularly above the melting or softening point of the polymer sample. The test stops at maximum temperature or when the space between the jaws reaches 65 mm.

Melting index [172] The melting index, or I ₂ , is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg for polymers based on polyethylene. Melt index, or Ii ₀ for polyethylene is also sometimes measured according to ASTM D 1238, Condition 190 ° C / 10 kg. The melt flow rate for polypropylene is typically measured according to ASTM 1238, Condition 230 ° C / 2.16 kg.

ATREF [173] Analytical fractionation analysis by increasing analytical temperature (ATREF) is conducted using the method described in U.S. Patent No. 4,798,081 and Wilde; L, Ryle, T.R .; Knobeloch, D.C .; Peat, I.R .: Determination of

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Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym Sci., 20, 441-455 (1982), which are incorporated herein in full by reference. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column slowly

increasing The temperature of solvent (trichlorobenzene) eluting in 20 to 120 ° C at a rate 1.5Â ° C / min. Analyze in NMR from C ¹³ [174] At samples are prepared adding

approximately 3 g of a 50/50 mixture of tetrachloroethane-d ² / orthodichlorobenzene to 0.4 g of sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 ° C. Data is collected using a JEOL ECLIPSE ^MR 400 MHz spectrometer or a 400MHz Varian Unity PLUS ^MR spectrometer, corresponding to a C ¹³ resonance frequency of 100.5 MHz. Data is acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve a minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum file size of 32K data points. The samples are analyzed at 130 ° C in a 10 mm wide band probe. Comonomer incorporation is determined using Randall's triad method (Randall, JC, JMS-Ver. Macrom.

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Chem. Phys., C29, 201-317 (1989), which is incorporated herein in its entirety by reference.

TREF Polymer Fractionation [175] Large-scale TREF fractionation is performed by dissolving 15-209 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB), stirring for 4 hours at 160 ° C. The polymer solution is forced by nitrogen at 100 kPa (15 psig) into a 7.6 cm x 12 cm (3 inch by 4 foot) steel column loaded with a 60:40 (v: v) bead mixture of technical quality glass, spherical with 600 - 425 pm (30 - 40 mesh) (commercially available from Potters Industries, HC Box 20, Brownwood, TX, 76801) and 0.7 diameter stainless steel wire shot mm (0.028) (commercially available from Pellets, Inc. 63 Industrial Drive, North Tonawanda, NY 14120). The column is immersed in a thermally controlled oil jacket, initially set at 160 ° C. The column is first cooled ballistically to 125 ° C, then slowly cooled to 20 ° C at 0.04 ° C per minute and held for one hour. Fresh TCB is introduced at about 65 ml / min while the temperature is increased to 0.167 ° C per minute.

[176] Portions of approximately 2000 mL of eluent from the preparative TREF column are collected in a heated 16-station fraction collector. The polymer is concentrated in each fraction using a rotary evaporator until about 50 to 100 ml of the polymer solution remains. The concentrated solutions are left to stand overnight before adding excess methanol, filtering, and rinsing (approx. 300-500 mL of methanol including the final rinse). The filtration step is carried out at a filtration station

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81/126 vacuum assisted 3 position using filter paper

5.0 µm coated with polytetrafluoroethylene (commercially available from Osmonics Inc., Cat # Z50WP04750). The filtered fractions are dried overnight in a vacuum oven at 60 ° C and weighed on an analytical balance before further testing.

Cast Resistance (MS) [177] The resistance of molten (MS) is measure using one rheometer adapted capillary with one matrix with 2.1 mm in diameter, 20: 1 matrix common angle input in

approximately 45 degrees. After equilibrating the samples at 190 ° C for 10 minutes, the piston is operated at a speed of 2.54 cm / minute (1 inch / minute). The standard test temperature is 190 ° C. The sample is extracted uniaxially to a set of accelerator nipples located 100 mm below the matrix with an acceleration of 2.4 mm / sec ² . The required tractive force is recorded as a function of the pick speed of the nip rollers. The maximum tensile strength obtained during the test is defined as the melt strength. In the event that the polymer melt exhibits plug resonance, the tensile strength before the plug resonance emerged was adopted as the melt resistor. The melt strength is recorded in centiNewtons (cN).

Catalysts [178] The term overnight, if used, refers to a time of approximately 16-18 hours, the term room temperature refers to a temperature of 2025 ° C, and the term mixed alkanes refers to to a commercially obtained mixture of commercially available C6-g aliphatic hydrocarbons under the trade name Isopar

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E®, from ExxonMobil Chemical Company. If the name of any compound here does not match its structural representation, the structural representation will prevail. The synthesis of all metal complexes and the preparation of all verification experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and were dried before use.

[179] MMAO refers to modified methylalumoxane, a commercially available triisobutylaluminum modified methylalumoxane from Akzo-Nobel Corporation.

[180] The preparation of the catalyst (Bl) was carried out as follows.

a) Preparation _______ of ________ (1-methylethyl) (2-hydroxy-3,5-di (tbutyl) phenyl) methylimine [181] 3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 ml of isopropylamine. The solution quickly turns bright yellow. After stirring slowly at room temperature for 3 hours, volatiles are removed in vacuo to [produce a crystalline, bright yellow solid (97 percent yield).

b) Preparation of 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl [182] A solution of (1- methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) imine (605 g, 2.2 mmol) in 5 mL of toluene is slowly added to a solution of Zr (CH2Ph) ₄ (500 mg, 1 , 1 mmol) in 50 mL of toluene. The resulting dark yellow solution is stirred slowly over 30 min. Solvent is removed under reduced pressure to produce the desired product as a reddish brown solid.

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83/126 [183] The preparation of the catalyst (B2) is carried out as follows.

a) Preparation of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5di (t-butyl) phenyl) imine [184] 2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 ml), and di-t-butylsalicylaldehyde (10.00 g, 42.67 mmoles) is added. The reaction mixture is stirred slowly over three hours and then cooled to 25 ° C over 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 ml), and then dried under reduced pressure. The yield is 11.17 g of a yellow solid. The NMR of H ¹ is consistent with the desired product as a mixture of isomers.

b) Preparation of bis- (1- (2-methylcyclohexyl) ethyl)) (2-oxoyl-

3.5- di (t-butyl) phenyl) imino) zirconium dibenzyl [185] A solution of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-

3.5- di (t-butyl) phenyl) imine (7.63 g, 23.2 mmoles) in 200 ml of toluene is slowly added to a solution of Zn (CH2Ph) ₄ (5.28 g, 11.6 mmoles) in 600 mL of toluene. The resulting dark yellow solution is stirred slowly for 1 hour at 25 ° C. The solution is further diluted with 680 ml of toluene to give a solution having a concentration of 0.00783 M.

[186] Cocatalyst 1 A mixture of methyldi (C14-18 alkyl) ammonium from tetrakis borate (pentafluorfenil) (hereinafter armenium borate), prepared by the reaction of a trialkylamine (Armeen ^MR M2HT, commercially available from Akzo-Nobel , Inc.), HCI and Li [B (CsF ₅ ) ₄ ], substantially as disclosed in US Patent No. 5,919,9883, ex. 2.

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84/126 [187]

Cocatalyst 2 Bis (tris (pentafluorfenyl) -aluminum) -2-undecylimidazolide (C4-is) dimethylammonium salt, mixed according to U.S. patent No. 6,395,671,

16.

[188]

Transfer agents. The transfer agents employed include diethylzinc (TEN, SAI), di (i-butyl) zinc (SA2), di (n-hexyl) zinc (SA3), triethyl aluminum (TEA, SA4).

trioctyl aluminum (SA5), triethyl aluminum (SA6), i-butyl aluminum bis (dimethyl (t-butyl) siloxane) (SA7), i-butyl aluminum bis (di (trimethylsilyl) amide) (SA8), n-octyl aluminum di (pyridine-2 -methoxide) (SA9), bis (n-octadecyl) ibutyl aluminum (SAIO), i-butyl aluminum bis (di (n-pentyl) amide) (SA11), n-octyl aluminum bis (2,6-di-t-butylphenoxide) (SA12), n-octyl aluminum di (ethyl (naphthyl) amide) (SA13), ethyl aluminum bis (t-butyldimethylsiloxide) (SA14) ethyl aluminium di (bis (trimethylsilyl) amide) (SA15), ethyl aluminum bis (

2,3,6,7-dibenzo-l-azacycloheptanoamide) (SAI 6), noctilaluminio bis (2,3,6,7-dibenzo-l-azacycloheptanoamide) (SA17), n-octyluminium bis (dimethyl (t-butyl ) siloxide) (SA18), ethylzinc (2,6-dipheniphenoxide) (SA19), and ethylzinc (tbutoxide) (SA20).

Examples 1-4, Comparison A-C

General Conditions for High Speed Parallel Polymerization [189]

Polymerizations are conducted using a high speed production parallel polymerization (PPR) reactor, commercially available from Symyx Technologies,

Inc., and operated substantially in accordance with patents

US ^Nos 6,248,540, 6,030,917, 6,362.309, and 6,306,658

6,316,663. Ethylene copolymerizations are conducted at 130 ° C and 1.4 MPa (130 ° C) with ethylene on demand used 1,2

Petition 870180058060, of 07/04/2018, p. 92/156

85/126 equivalent of cocatalyst 1 based on the total catalyst used (1.1 equivalents when MMAO is present). A series of polymerizations are carried out in a parallel pressure reactor (PPR) consisting of 48 individual reactor cells in a 6 x 8 arrangement that are provided with a pre-weighed glass tube. The working volume in each reactor cell is 6000 gL. Each cell has temperature and pressure controlled with agitation provided by individual stirring paddles. The monomer gas and the quick-cooling gas are piped directly to the PPR unit and controlled by automatic valves. Liquid reagents are robotically added to each reactor cell using syringes and the reservoir solvent is mixed alkanes. The order of addition is mixed alkanes (4 mL), ethylene, 1-octene comonomer (1 mL), cocatalyst 1, or mixture of cocatalyst 1 / MMAO, transfer agent, and catalyst or mixture of catalysts. When a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts is used, the reagents are pre-mixed in a small flask just before addition to the reactor. Although a reagent is omitted in an experiment, the order of addition above is maintained. The polymerizations are carried out for approximately 1-2 minutes, until predetermined ethylene consumption is reached. After rapid cooling with CO, the reactors are cooled and the glass tubes are discharged. The tubes are transferred to a centrifugal / vacuum dryer unit, and dried for 12 hours at 60 ° C. The tubes containing dry polymer are weighed and the tare weight gives the net polymer yield. The results are contained in table 1. In table 1 and other locations in the order,

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86/126 comparative compounds are indicated by an asterisk (*).

[190] Examples 1-4 demonstrate the synthesis of linear block copolymers by the present invention as evidenced by the formation of an essentially monomodal copolymer with very narrow MWD TEN is present and a product with a wide molecular weight distribution, bimodal (a mixture of separately produced polymers) in the absence of TEN. Due to the fact that the catalyst (Al) is known to incorporate more octene than the catalyst (Bl), the different blocks or segments of the copolymers resulting from the invention are distinguishable based on branching or density.

Petition 870180058060, of 07/04/2018, p. 94/156

87/1 26

87/126 Abela 1

rd ω Φ ι — 1 -Η X φ b 1 LO κ CX] LT) LT) 00 κ τ — 1 <ο Ç CX] CX] Μ ο ΟΊ CX] ϊ — 1 σι CX] C0 ϊ — 1 τ — 1 Γ- LO κ κ κ κ κ κ σι ϊ — 1 LT) ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 Ç 300502 36957 45526 | 28715 2161 22675 3338 ο 4-> Φ σ> ϊ — 1 00 00 00 ΟΊ Φ <ο 00 σι Γ- <ο Γ- AND tn σι LT) Ο οί CX] 00 Η τ — 1 τ — 1 CX] ϊ — I τ — 1 τ — 1 B κ κ κ κ κ r — í κ ç Ο Ο Ο Ο Ο Ο φ ο Ο κ Ο Ο κ ω c; ι — 1 00 Ο κ Ο Φ ο | | I 00 00 00 Φ S-l Η ί TEN TEN ( ΤΕΑ ( ΤΕΑ ( ο ι — 1 0 σ> LO 00 κ κ κ 1 1 1 1 ί Ο Ο Ο <Ο Ο <ο CX] CX] CX] CX] Ο ο ο υ 0 you <Ο τ — 1 Γ- οί οί οί οί Ο τ — 1 τ — 1 ϊ — I ϊ — I ϊ — I ϊ — I s κ κ κ κ κ κ κ Ο Ο Ο Ο Ο Ο Ο τ — 1 PQ ι — 1 0 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 1 κ κ κ κ κ κ • s Ο Ο Ο Ο Ο Ο 4-> Φ Ο τ — 1 ι — 1 <ο <ο <ο <ο <ο <ο ο ο | ο ο ο ο ο 6 κ κ κ κ κ κ 4-> 3. Ο Ο Ο Ο Ο Ο Φ Ο Εχ. * * PQ * Ο ϊ — 1 CX] σ>

ω Ο Φ Ο b

S-l ο ο ο ο

S-l ο ίλ s-l ο

-Η

S-l Φ ίλ ω

Ο υ

ω Φ -Η

Φ Ό

Φ Ο

Φ Ό

S-l

Ο Φ Η

S-l Φ ι — I

Φ Ο φ ι — I ο

Ê ο ω φ ίλ φ Ό ι — I Φ Ό

Ο Ê -Η b

Ο ίφ

Ο -Η

Φ b -Η

S-l 4-> ω -Η Q

Petition 870180058060, of 07/04/2018, p. 95/156

88/126 [191] It may be seen that the polymers produced according to the invention have a relatively narrow polydispersity (M _w / M _n ) and a higher block copolymer content (trimer, tetramer, or higher) than polymers prepared in the absence of the transfer agent.

[192] Additional characterizing data for the polymers in Table 1 are determined with reference to the figures. More specifically, the DSC and ATREF results show the following:

[193] The DSC curve for the polymer of example 1 shows a melting point (T _m ) of 115.7 ° C with a melting heat of 158.10 J / g. The corresponding CRYSTAF curve shows the peak

higher at 34.5 ° C with an area peak in 52.9 per cent. THE difference between T _m per DSC and the Tcrystaf is in 81.2 ° C. [194] The curve of DSC to polymer of example 2 shows

a peak with a melting point (T _m ) of 109.7 with a melting heat of 214.0 ° CJ / g. The corresponding CRYSTAF curve shows the highest peak at 46.2 ° C with a peak area of 57.0 percent. The difference between T _m by DSC and T _CRYSTAF is 63, 65 ° C.

[195] The DSC curve for the polymer of example 3 shows a peak with a melting point (T _m ) of 120.7 ° C with a melting heat of 160.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 66.1 ° C with a peak area of 71.8 percent. The difference between T _m by DSC and T _CRYSTAF is 54.6 ° C.

[196] The DSC curve for comparative example A * shows a melting point (T _m ) of 90.0 ° C with a melting heat of 86.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 48.5 ° C with a peak area of 29.4 percent. Both of these values are consistent with a resin that is

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89/126 low density. The difference between T _m by DSC and T _CRYSTAF is 41.8 ° C.

[197] The DSC curve for comparative B shows a melting point (T _m ) of 129.8 ° C with a melting heat of 237.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 82.4 ° C with a peak area of 83.7 percent. Both of these values are consistent with a resin that is high in density. The difference between T _m by DSC and T _CRYSTAF is 47.4 ° C.

[198] The DSC curve for comparative C shows a melting point (T _m ) of 125.3 ° C with a melting heat of 143.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C with a peak area of 34.7 percent and the lowest crystalline peak at 52.4 ° C. The separation between these two peaks is consistent with the presence of a polymer with high crystallinity and one with low crystallinity. The difference between T _m by DSC and T _CRYSTAF is 43.5 ° C.

Examples 5-19, Comparatives D * -F *, Continuous Solution Polymerization, Catalyst A1 / B2 + TEN [199] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Mixed alkanes solvent (Isopar ^MR E commercially available from ExxonMobil Chemical Company), ethylene at 1.22 kg / hour (2.70 lbs / hour), 1-octene, and hydrogen (when used) are supplied to a 3 , 8 L equipped with a jacket for temperature control and an internal thermocouple. The solvent supply to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the reactor pressure. Upon discharge from the pump, a

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90/126 side current is taken to provide cleaning flows for the catalyst and cocatalyst 1 lines and the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (when used) and fed to the reactor. A mass flow controller is used to supply hydrogen to the reactor as needed. The temperature of the solvent / monomer solution is controlled with the use of a heat exchanger before the reactor enters. This current enters the bottom of the reactor. Component solutions of the catalyst are measured using pumps and flow meters and are combined with the catalyst wash solvent and introduced into the reactor bottom. The reactor is operated filled with liquid at 3.45 MPa (500 psig) with vigorous agitation. Product is removed from the outlet lines at the top of the reactor. All reactor output lines are followed by steam and isolated. Polymerization is stopped by adding a small amount of water into the outlet line along with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder and a water-cooled pelletizer. Process details and results are contained in table 2. Selected polymer properties are provided in table 3.

Petition 870180058060, of 07/04/2018, p. 98/156 / 1 26

ω Ο> -Η -Ρ Φ

Ο -Η Μ-ι -Η ι — I

Φ X ω ω Ο Ρ Φ 6 Ή ι — I

Ο CU φ 75

Ο ίφ ο φ Ρ φ ίλ φ Ρ CU φ

φ Ρ φ ίλ ο ω ω φ υ ο Ρ Ρπ φ 75 ω Φ Π ι — I

Φ -Ρ Φ Q

CM

Φ ι — I

Φ

Π

Φ Η

ο -Η u-i κ [ 95.2 126.8 257.7 118, 3 C0 ϊ — 1 244, 1 261, 1 267, 9 131, 1 100.6 137, 0 161, 9 114, 1 121, 3 159.7 155.6 90.22 O LO o ϊ — 1 75 Η ω ο C0 C0 C0 t — 1 ϊ — 1 kD 00 00 t — 1 t — 1 CO CO CO CO CO O 00 xT 1—1 ο \ ° ϊ — 1 ϊ — 1 ο ϊ — 1 ϊ — 1 Ο ο ο ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 00 00 ω ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 > ’ <ο 00 σ> LO kD C0 C0 ο co ϊ — 1 co ϊ — 1 co co o LO co poo ϊ — 1 ϊ — 1 00 o co σ> C ο ο ο \ ° 00 00 00 00 00 00 σ> 00 σ> 00 ο ο o σ> o σ> o σ> σ> 00 00 σ> 00 O σ> 00 σ> 00 o σ> ίθ LD Η η ϊ — 1 LT) LD ο C0 co 00 O σ> ϊ — 1 O 00 LD LD LO X ι — 1 tP 00 LT) L0 L0 L0 L0 L0 LO LO LO 00 co ϊ — 1 ίθ ο Λ Ε-η X ϊ — 1 ϊ — ι ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 L0 LT) σ> ο 00 00 , - | 3596 | LD LO co LD co LD LO ϊ — 1 ω Q C0 00 ϊ ϊ — ι ϊ — 1 ϊ — 1 σ> LD 00 00 O co LO ο LT) LD co co LO co co LD co co ¹ - ¹ ο X φ -Ρ ο η Ο \-1 L0 00 C0 C0 00 O LD O σ> O 00 ϊ — 1 ϊ — 1 C0 ϊ — 1 ϊ — 1 ϊ — 1 O ϊ — 1 O O ϊ — 1 O O ϊ — 1 O Λ Χι ο ο ο ο Ο ο ο ο O O O O O O O O O ο C -Ρ ο -Αο 820 | C0 co co co CO co co co co co co ο ο O \ ^w ** ** ** ** ** ** ο ο ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ο X φ Ν ω η C0 C0 C0 LD ο σ> LD σ> LD O 00 ϊ — 1 σ> C0 1 C0 C0 ϊ — 1 ο ϊ — 1 ϊ — 1 O O ϊ — 1 ϊ — 1 O O ϊ — 1 O Λ X Q ο ο ο ο ο ο O O O O O O O O O O ο Ν ω O Ç ο \ ο ϊ — I ϊ — I 1 ϊ — 1 ϊ — 1 ϊ — 1 co 00 0 ο ο ο ο ο ο O O ο X φ η ο L0 C0 00 L0 LO σ> co co 4_) C0 PQ _ 1 ϊ — 1 Ο ϊ — 1 ο Ο ϊ — 1 ϊ — 1 O O co ϊ — 1 ϊ — 1 ϊ — 1 co ο Λ X ο Ο ο ο Ο O O O O O O O O O C0 PQ σ> 00 00 χΓ 00 co Ρ ο 0.00 to 1 ο ϊ — I Ο C0 ο C0 ο C0 Ο C0 the co ο X φ η L0 ο LO co LO LD co LD O O LO 4_) ϊ — 1 < _ ϊ — 1 1 Ο ϊ — 1 ϊ — 1 Ο ο ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 O ϊ — 1 ϊ — 1 ϊ — 1 O ο Λ X ο Ο ο ο Ο ο O O O O O O O O O C0 xT Ρ ο ϊ — 1 < Ε SX a CXJ C0 1 ϊ — 1 ? f ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ο ο co O ϊ — 1 co O co ϊ — 1 ϊ — 1 co Ε-η ο χ — χ C0 ϊ ç co co co co co ç co co co co ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 ϊ — 1 - CXJ X C Η co t — 1 9, 90 ο ο 51, 6 C0 ο 6.90 co 00 the o (cm C0 LT) C0 C0 co O > ’ LO C0 Γ — I 0 ω φι Λ C0 ϊ — 1 ϊ — 1 ϊ — 1 ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** <ο t — 1 X co (kg / h C0 L0 _{f f f f f f f f f f f} LD _{f f} LO poo ο ι — 1 CO O O Εχ • * Q * W * [XJ LO kD 00 o ϊ — 1 ϊ — 1 ϊ — 1 co ϊ — 1 co ϊ — 1 ϊ — 1 LD ϊ — 1 LO ϊ — 1 ϊ — 1 00 ϊ — 1 σ> ϊ — 1

> C -Η

Φ

Ο ι — I

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Ç

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CX]

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92/126

CN σ>

S-ι Ν tn a S-i O tn 4-> <tJ II Φ S4 S o tn C

Φ Ο Ό c Φ o — I H S 4-> Φ tn

Φ O Ό S-i

Ω ω h n O Φ Sd>

C Φ Ο Ό O tn

Φ Λ!

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4-> c c <Φ φ -H o o

5- I -H φ 4-1 Sd Φ

Area Peak CRYSTAF o \ ° 66 95 20 09 63 29 13 16 52 25 91 00 92 10 57 57 00 00 1 Ê H t- | Eh £ o ° O EH l> 45 47 72 71 72 43 75 74 83 83 00 82 73 73 50 45 t- | Eh ω ω H O o 30 r * 78 00 O 00 81 41 40 30 30 73 32 43 43 The r * O 00 the H O o 45 113 111 101 103 106 109 92 93 O 00 O 00 106 91 LO LO 106 112 ε H O o 37 124 125 120 115 121 124 125 116 114 113 114 121 114 117 116 120 125 Heat Fusion Cn • d 32 183 06 55 55 LO 89 74 54 63 40 CX] K 123 33 43 43 136 169 ç X O O 00 O t — 1 CX] CX] LO 00 00 t — 1 O O O 5 K CX] K CX] co τ — 1 K CX] K CX] K CX] K co K K t — 1 K t — 1 K t — 1 K CX] K t — 1 K CX] K CX] K CX] K t — 1 K t — 1 ç ι — 1 O Ê O O 00 .300 O 00 ΟΊ .200 .300 .100 .100 .700 .200 .500 .100 . 600 . 600 .100 O O O O O O O O O tn 55. 33. 53. 53. 53. O 28. 58. 36. 55. 63. 43. O r * LO 37. 39. ι — £ 1 0 O o o O o o .300 . 600 . 600 .500 o o o . 600 .100 200 .500 .100 O o the o .500 .500 O o o O o 00 tn 110 65. 137 104 109 118 129 129 113 LO LO 101 132 81. r * 148 107 72. LO r * CM H LO LO l> LO t — 1 l> t — 1 LO LO LO O t — 1 00 t — 1 O o t — 1 H K LO K LO co τ — 1 K LO K LO K r * r * K K LO K LO K LO K LO K LO K LO K r * K LO K LO K LO O O O LO 00 LO CX] 00 l> LO CX] CX] LO LO co co t — 1 H O τ — 1 co 12, K ΟΊ K r * K r * K LO K ΟΊ K r * LO co τ — 1 LO τ — 1 t — 1 co 11, CX] 20, LO O LO t — 1 O ΟΊ t — 1 CX] t — 1 t — 1 l> LO O LO l> t — 1 H K t — 1 K r * K O K t — 1 K t — 1 K t — 1 K O K t — 1 K t — 1 K K CX] K O K CX] K LO K O K t — 1 K K co Φ T5 ok H CO AND O 8627 9378 8895 8786 8785 8825 00 CX] 00 00 8836 8784 8818 8700 8718 9116 8719 8758 8757 9192 9344 d) tn K O K O K O K O K O K O K O K O O O O O O O O O O O Q Ex. * Q * * LO LO l> 00 10 11 12 13 14 15 16 17 18 19

The tn3 t> C Φ> c -H

Ό

The ι — I

Φ X Φ 'Φ o tn3 c

o> -H

4-> Φ

5- I

U

Petition 870180058060, of 07/04/2018, p. 100/156

93/126 [200] The resulting polymers are tested by DSC and ATREF as in the previous examples. The results are as follows.

[201] The DSC curve for the polymer of example 5 shows a peak with a melting point (T _m ) of 119.6 ° C with a melting heat of 60.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 47.6 ° C with a peak area of 59.5 percent. The delta between T _m by DSC and T _CRYSTAF is 72.0 ° C.

[202] The DSC curve for the polymer of example 6 shows a peak with a melting point (T _m ) of 115.2 ° C with a melting heat of 60.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 44.2 ° C with a peak area of 62.7 percent. The delta between T _m by DSC and T _CRYSTAF is 71.0 ° C.

[203] The DSC curve for the polymer of example 7 shows a peak with a melting point (T _m ) of 121.3 ° C with a melting heat of 69.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 49.2 ° C with a peak area of 29.4 percent. The delta between T _m by DSC and T _CRYSTAF is 72.1 ° C.

[204] The DSC curve for the polymer of example 8 shows a peak with a melting point (T _m ) of 123.5 ° C with a melting heat of 67.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.1 ° C with a peak area of 12.7 percent. The delta between T _m by DSC and T _CRYSTAF is 43.4 ° C.

[205] The DSC curve for the polymer of example 9 shows a peak with a melting point (T _m ) of 124.6 ° C with a melting heat of 73.5 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.8 ° C with a peak area of 16.0 percent. The delta between T _m by DSC and T _CRYSTAF is 43.8 ° C.

[206] The DSC curve for the polymer of example 10 shows a peak with a melting point (T _m ) of 115.6 ° C with a heat of

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94/126 melting at 60.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.9 ° C with a peak area of 52.4 percent. The delta between T _m by DSC and T _CRYSTAF is 7 4.7 ° C.

[207] The DSC curve for the polymer of example 11 shows a peak with a melting point (T _m ) of 113.6 ° C with a melting heat of 70.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 39.6 ° C with a peak area of 25.2 percent. The delta between T _m by DSC and T _CRYSTAF is 7 4.1 ° C.

[208] The DSC curve for the polymer of example 12 shows a peak with a melting point (T _m ) of 113.2 ° C with a melting heat of 48.9 J / g. The corresponding CRYSTAF curve shows the peak at or above 30 ° C. (AT _CRYSTAF for further calculation purposes is then set at 30 ° C). The delta between T _m by DSC and Tcr _Y staf is 83.2 ° C.

[209] The DSC curve for the polymer of Example 13 shows a peak with a melting point (T _m ) of 114.4 ° C with a melting heat of 49.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 33.8 ° C with a peak area of 7.7 percent. The delta between T _m by DSC and T _CRYSTAF is 84.4 ° C.

[210] The DSC curve for the polymer of example 14 shows a peak with a melting point (T _m ) of 120.8 ° C with a melting heat of 127.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 72.9 ° C with a peak area of 92.2 percent. The delta between T _m by DSC and T _CRYSTAF is 47.9 ° C.

[211] The DSC curve for the polymer of example 15 shows a peak with a melting point (T _m ) of 114.3 ° C with a melting heat of 36.2 J / g. The corresponding CRYSTAF curve shows the highest peak at 32.3 ° C with a peak area of 9.8 percent. The delta between T _m by DSC and T _CRYSTAF is 82.0 ° C.

[212] The DSC curve for the example 16 polymer shows

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95/126 a peak with a melting point (T _m ) of 116.6 ° C with a melting heat of 44.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 48.0 ° C with a peak area of 65.0 percent. The delta between T _m by DSC and T _CRYSTAF is 68.6 ° C.

[213] The DSC curve for the polymer of example 17 shows a peak with a melting point (T _m ) of 116.0 ° C with a melting heat of 47.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 43.1 ° C with a peak area of 56.8 percent. The delta between T _m by DSC and T _CRYSTAF is 72.9 ° C.

[214] The DSC curve for the polymer of example 18 shows a peak with a melting point (T _m ) of 120.5 ° C with a melting heat of 141.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 70.0 ° C with a peak area of 94.0 percent. The delta between T _m by DSC and T _CRYSTAF is 50.5 ° C.

[215] The DSC curve for the polymer of example 19 shows a peak with a melting point (T _m ) of 124.8 ° C with a melting heat of 174.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.9 ° C with a peak area of 87.9 percent. The delta between T _m by DSC and T _CRYSTAF is 45.0 ° C.

[216] The DSC curve for comparative D polymer shows a peak with a melting point (T _m ) of 37.3 ° C with a melting heat of 31.6 J / g. The corresponding CRYSTAF curve shows no peak at or above 30 ° C. Both of these values are consistent with a resin that is low in density. The delta between T _m by DSC and T _CRYSTAF is 7.3 ° C.

[217] The DSC curve for comparative E polymer shows a peak with a melting point (T _m ) of 124.0 ° C with a melting heat of 179.3 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.3 ° C with a peak area of 94.6 percent. Both of these values are consistent

Petition 870180058060, of 07/04/2018, p. 103/156

96/126 with a resin that is high in density. The delta between T _m by DSC and T _C rystaf is 44.6 ° C.

[218] The DSC curve for comparative F polymer shows a peak with a melting point (T _m ) of 124.8 ° C with a melting heat of 90.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 77.6 ° C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystallinity and a low crystallinity polymer. The delta between T _m by DSC and

Tcrystaf is 47.2 ° C.

Physical Property Tests [219]

Polymer samples are evaluated for physical properties such as high temperature resistance properties, as evidenced by TMA temperature tests, pellet blocking resistance, high temperature recovery, permanent deformation by high temperatures, and storage module ratio,

G '(25 ° C) / G' (100 ° C).

Several commercially available polymers are included in the tests: the comparative example G * is a substantially linear ethylene / l-octene copolymer (AFFINITY®, commercially available from The Dow Chemical Company), the comparative example H * is an ethylene / l copolymer - substantially linear, elastomeric octene (AFFINITY® EG8100, commercially available from The Dow Chemical Company), comparative example I * is a substantially linear ethylene / l-octene copolymer (AFFINITY® PL1840, commercially available from The Dow Chemical Company), comparative example J * is a tri-block copolymer of styrene / butadiene / hydrogenated styrene (KRATON ^mr G1652, commercially available from KRATON

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Polymers), the comparative example K * is a thermoplastic vulcanized product (TPV, a mixture of polyolefins containing a crosslinked elastomer dispersed therein). The results are shown in table 4.

Table 4 Mechanical Properties at High Temperature

Ex. Penetration TMA-1 mm (° C) Res. Bloc. Pellets kPa (lb / ft ² ) G '(25 ° C / G '(100 ° C) Recup. Def. 300% (80 ° C) (Percent) Def. Perman. (70 ° C) (percent) D * 51 - 9 Failed - AND* 130 - 18 - - F * 70 6.8 (141) 9 Failed 100 5 104 0 (0) 6 81 49 6 110 - 5 - 52 7 113 - 4 84 43 8 111 - 4 Failed 41 9 97 - 4 - 66 10 108 - 5 81 55 11 100 - 8 - 68 12 88 - 8 - 79 13 95 - 6 84 71 14 125 - 7 - - 15 96 - 5 - 58 16 113 - 4 - 42 17 108 0 (0) 4 82 47 18 125 - 10 - - 19 133 - 9 - - G * 75 22.2 (463) 89 Failed 100 H* 70 10.2 (213) 29 Failed 100 I * 111 - 11 - - J * 107 - 5 Failed 100 K * 152 - 3 - 40

[220] In table 4, the comparative example F * (which is a physical mixture of the two polymers resulting from simultaneous polymerizations using catalysts Al and Bl) has a penetration temperature of 1 mm of about 70 ° C, whereas examples 5 to 9 have a penetration temperature 1 mm of 100 ° C or higher. In addition, examples 10 to 19 all have a penetration temperature of 1 mm of around 85 ° C, with the

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98/126 majority having a penetration temperature 1 mm greater than 90 ° C or even greater than 100 ° C. This shows that the new polymers have better dimensional stability at higher temperatures compared to a physical mixture. The comparative J * (a commercial SEBS) has a good 1 mm TMA temperature of around 107 ° C, plus it has a very poor permanent deformation (high temperature 70 ° C) of around 100 percent and also failed to recover (the sample broke) during a high temperature (80 ° C), recovery from deformation at 300%. Therefore, the exemplified polymers have a unique combination of properties not available even in some commercially available high performance thermoplastic elastomers.

[221] Similarly, table 4 shows a low (good) ratio of storage module, G '(25 ° C) / (G' (100 ° C), for the inventive polymers of 6 or less, while a mixture physics (comparative F *) has a storage module of 9 and a random ethylene-octene copolymer (comparative G *) of similar density has a storage module ratio of an order of magnitude greater (89). of a polymer's storage module is as close as possible to 1. Such polymers will not be relatively affected by temperature, and manufactured articles made of such polymers can be usefully employed over a broader temperature range. Storage module and temperature independence is particularly useful in elastomer applications such as pressure sensitive adhesive formulations.

[222] The data in Table 4 also shows that the

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99/126 polymers of the invention have improved pellet blocking resistance. In particular, example 5 has a pellet blocking resistance of 0 MPa, meaning that it is free flowing under the conditions tested, compared to comparisons F and G that show considerable blocking. Blocking resistance is important since bulk polymer transport having high blocking resistances may result in the product clumping or sticking to storage or transportation, resulting in poor handling properties.

[223] Permanent compression deformation at high temperatures (70 ° C) for the inventive polymers is generally good, generally meaning less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent cent. In contrast, comparisons F *, G *, H * and J *, all show a permanent compression strain at 70 ° C of 100 percent (the maximum possible value, indicating no recovery). Good permanent compression deformation at high temperatures is especially necessary for applications such as gaskets, window profiles, o-rings, and the like.

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100/126 ω

4-> C Φ Η η φ

Φ 4-) Φ

ω Φ υ -Η

Φ <φ υ φ S ω Φ Ό

Φ Ό

Φ -Η d Ο 14 CU

14)

Φ ι — I

Φ Π

Φ Η

Relax. Strain to 50% Deform l 1 1 33 1 1 1 1 1 30 1 1 1 1 1 1 1 1 50 1 1 1 1 Deform Perman. 21 ° C (%) 1 1 42 14 13 20 22 25 12 14 17 21 1 14 13 'xT 1 1 27 23 1 25 30 Tension Retract at 150% Def. (KPa ) 760 1 O o 790 861 810 760 1 098 510 700 1 1 770 1040 920 1 1 110 O 00 co 1 1900 1 Recup. Deform. 300% a 21 ° C (%) 83 1 65 74 75 73 74 1 75 kO 75 1 1 83 83 83 1 1 53 09 1 kO 1 Recup. Deform. 100% a 21 ° C (%) 91 1 78 87 1 82 82 1 kO 00 68 91 91 1 68 00 00 13 1 1 kO 00 87 1 93 1 Trat. Notch Resit. Rip. 1 1 339 1 1 1 461 1 1 976 1247 691 1 2074 1 1274 1 1 746 569 1 1 1 Abrasion Loss Vol. (Mm ³ ) 1 1 93 00 1 39 45 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Along. Break (%) 1074 1029 824 1116 938 854 810 823 902 1090 931 814 857 1573 896 1252 00 o 00 871 1000 829 697 609 1 Resist Tract a (MPa) 10 31 12 16 14 14 14 12 14 16 13 13 29 10 12 13 30 36 17 15 29 32 1 Along. Break (%) 1 1 1 951 1 kO 00 785 1 1 1 961 1 1 1127 1 1 1 1 1 1 1 1 1 Resist Tract a (MPa) 1 1 1 14 1 15 13 1 1 1 12 1 1 12 1 1 1 1 1 1 1 1 1 Module Tract (MPa) LO 589 kO 24 29 37 35 38 23 26 17 14 160 14 20 18 239 483 15 15 147 1 1 Module Flex. (MPa) 12 895 57 30 33 'xT 41 43 23 30 20 16 212 18 23 20 323 706 15 16 210 1 1 Ex * Q * * LO kO 00 CT) 10 11 12 13 14 15 16 17 18 19 * O * * H * • d *

ω Φ ο π

CN

Φ

4-)

C Φ

Φ Ό

U ο οο cn

Φ

Ο Ό -Η Ό

Φ S <Ν

CN CN

101/126 [225] Table 5 shows results of mechanical properties for the new polymers as well as for several comparative polymers at room temperatures. It can be seen that the inventive polymers have good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mm ³ , preferably less than 80 mm ³ , and especially less than about 50 mm ³ . In this test, higher numbers indicate higher loss of volume and, consequently, less resistance to abrasion.

[226] The tear strength as measured by the notched tractive tear strength of the inventive polymers is generally 1000 mJ or greater, as shown in table 5. The tear strength of the inventive polymers can be as high as 3000 mJ, or even as high as 5000 mJ. Comparative polymers generally have tear strengths not greater than 750 mJ.

[227] Table 5 also shows that the polymers of the invention have better refractive stress at a deformation of 150 percent (demonstrated by the higher refractive stress values) than some of the comparative samples. Comparative examples F *, G * and H * have values of refractive stress at 150 percent strain of 400 kPa or less, while inventive polymers have values of refractive stress at 150 percent strain of 500 kPa (e.g. 11) up to as high as 1100 kPa (ex. 17). Polymers having a refractive stress value of more than 150 percent would be quite useful for elastic applications, such as fibers and elastic fabrics, especially non-woven fabrics. Other applications include diapers, hygiene items, and strap applications for

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102/126 medical clothing, such as straps and elastic tapes.

[228] Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for inventive polymers compared, for example, with the G * comparison. Less stress relaxation means that the polymer retains its strength better in applications such as diapers and other garments where retention of properties over extended periods of time with body temperatures is desired. Optical Tests

Table 6 Optical Properties of Polymers

Ex. Internal Mist (%) Cleanliness (%) Brightness (%) P* 84 22 49 G * 5 73 56 5 13 72 60 6 33 69 53 7 28 57 59 8 20 65 62 9 61 38 49 10 15 73 67 11 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 61 22 60 19 74 11 52 G * 5 73 56 H* 12 76 59 I * 20 75 59

[229] The optical properties reported in Table 6 are based on compression-molded films substantially lacking orientation. The optical properties of the polymers can be varied over wide ranges, due to the variation in size of crystallites, resulting from the variation in the amount of chain transfer agent

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103/126 used in polymerization.

Extractions of Multiblock Copolymers [230] Extraction studies of the polymers of examples 5, 7 and comparative E * are conducted. In the experiments, the polymer sample is weighed in a fried glass extractor cone and placed in a Kumagawa type extractor. The extractor with the sample is purged with nitrogen, and a 500 ml round flask is loaded with 350 ml of diethyl ether. The vial is then fitted to the extractor. The ether is heated while being stirred. The time is noted when the ether begins to condense inside the cone, and the extraction is allowed to proceed under nitrogen for 24 hours. At this time, the heating is stopped and the solution is allowed to cool. Any ether remaining in the extractor is returned to the flask. The ether in the flask is evaporated under vacuum at room temperature, and the resulting solids are purged to dryness with nitrogen. Any residue is transferred to a heavy bottle using successive hexane washes. The combined hexane washes are then evaporated with another nitrogen purge, and the residue dried under vacuum overnight at 40 ° C. Any ether remaining in the extractor is purged to dryness with nitrogen.

[231] A second round-bottom flask loaded with 350 mL of hexane is then connected to the extractor. The hexane is heated to reflux with stirring and held at reflux for 24 hours after noticing the hexane starting to condense in the cone. Heating is then stopped and the flask is allowed to cool. Any hexane left in the extractor is transferred back to the bottle. The hexane is removed by vacuum evaporation at room temperature, and any residue remaining

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104/126 in the bottle is transferred to a heavy bottle using successive washes with hexane. The hexane in the flask is evaporated with a nitrogen purge, and the residue is vacuum dried overnight at 40 ° C.

[232] The polymer sample remaining in the cone after extractions is transferred from the cone to a heavy bottle and vacuum dried overnight at 40 ° C. The results are shown in table 7.

Table 7

Sample Weight (g) Soluble in Ether (g) Soluble in Ether (%) c ₈ Moles percent ¹ Soluble in Hexane (g) Soluble in Ether (%) c ₈ Moles percent ¹ Residue C ₈ percent P * 1.097 0.063 5.69 12.2 0.245 22.35 13, 6 6, 5 Ex. 5 1.006 0.041 4.08 - 0.040 3.98 14.2 11, 6 Ex. 7 1.092 0.017 1.59 13.3 0.012 1, 10 11.7 9.9

¹ Determined by C ¹³ NMR

Examples of Additional Polymers 19A-K, Continuous Solution Polymerization, Catalyst A1 / B2 + TEN [233] Continuous solution polymerizations are carried out in a well-mixed computer controlled reactor.

Solvent of alkanes mixed purified (Isopar ^MR AND commercially available from ExxonMobil, Inc .), ethylene, 1- octene, and hydrogen (When used) are combined and fed to a reactor of 27 gallons. At feeds to reactor are measures by controllers mass flow. THE

The temperature of the supply stream is controlled with the use of a glycol-cooled heat exchanger before entering the reactor. Catalyst component solutions are measured using pumps and mass flow meters. The reactor is operated filled with liquid at a pressure of approximately 550 psig. At the outlet of the reactor, water and additive are injected into the polymer solution. The water hydrolyzes the

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105/126 catalysts, and interrupts polymerization reactions. The post-reactor solution is then heated in preparation for two-stage devolatilization. The unreacted solvent and monomers are removed during the devolatilization process. The polymer melt is pumped into a die for underwater pellet cutting.

[234] Process details and results are contained in tables 8 and 8 (a). Properties of selected polymers are provided in tables 9 and 9 (a).

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Cone. Cocat CX] 1 uidd 525 525 525 525 525 525 525 525 1 ο X 4-> <η ο Λ LO cn t — 1 kO CX] t — 1 CX] O <o <o <o <o <o LO LO LO r * 1 ο υ rQ K K K K K K K K K ι — 1 O O O O O O O O O ο Cocat uidd O O O O O O O O O O O O O O O O O O ο υ LO LO LO LO LO LO LO LO LO ο X 3 ιχι ω Ê Οι O 'xT 'xT 'xT 'xT O CX] ΟΊ r * CX] kO cn O r * LO r * r * t — 1 Γ— | Q Pt K O K O K O K t — 1 K t — 1 K O K O K O K t — 1 K O Pt ο ιχι O O O O O O O O O LO Ç Μ et K K K K K K K K K K ο Q cn cn cn cn cn cn cn cn cn <O ο ο \ ° ο X 3 Β2 Ê ϋ CX] LO cn t — 1 O ΟΊ kO 'xT kO • LO kO <o <o <o LO <o r * cn Γ— | 4-> 01 υ it K O K O K O K O K O K O K O K O K O K O CX] ο PQ Ε O O O O O O O O O l> d et O O O O O O O O O <O r * 0 ο Μ (t Ct CX] CX] CX] CX] CX] CX] CX] CX] CX] υ Ο X 3 < ppm LO LO kO CX] t — 1 O ΟΊ t — 1 'xT CX] 4-> CX] CX] CX] CX] CX] CX] t — 1 CX] ç\] 01 υ K K K K K K K K ι — 1 O O O O O O O O O O ι — 1 ο < FÍ O O O O O O O O O O d d O O O O O O O O O LO 0 ο Η CD d kO kO <o <o <o <o <o <o <o t — 1 υ ο O O O O O O O O O O Η CX] CX] CX] CX] CX] CX] CX] CX] CX] CX] τ — 1 τ — 1 τ — 1 τ — 1 τ — 1 τ — 1 τ — 1 τ — 1 τ — 1 t — 1 OJ ΟΊ Μ Ê Ο min 101 577 550 09 251 124 188 58 53 47 cn co l> cn LO cn τ — 1 l> ΟΊ > Λ O cn cn r * cn <o τ — 1 LO kO K 325 K K K K K K K Ο QC Λ cn kO kO O LO 00 cn O ι — 1 CX] CX] CX] CX] cn CX] τ — 1 CX] LO cn cn cn cn cn cn cn cn cn kO r * 00 cn O 00 l> CX] 'xT Μ CM υ Λη O ΟΊ LO r * 00 O 00 O Λ K CX] K 00 K O K O K τ — 1 K K co K K K cn CX] cn cn cn cn cn cn cn ΟΊ LO cn cn LO cn LO LO CX] kO Μ CM υ Λη CX] LO 00 CX] τ — 1 O Α K LO K co K LO K K K O K kO K O K LO K LO LO LO LO LO LO LO LO LO _The < PQ u Q M tl O H • d X ΟΊ ΟΊ Μ t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1

Eff. ^B 297 295 293 280 00 00 CX] 319 333 312 275 1 . The 00 kO l> cn 'xT kO CX] IN O O co O K r * K r * r * K r * r * K r * r * r * r * 1 o \ o t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 X) O LOl „ ω O t — 1 ΟΊ t — 1 'xT LO LO O O K K K K K K K K K the et 00 00 00 00 00 r * r * 00 00 00 00 00 00 00 00 00 00 00 c ^oX ° O u AND H ι — 1 O CX] cn kO t — 1 t — 1 CX] t — 1 cn ft \ r * t — 1 LO t — 1 cn r * CX] <o K K K K K K K 1 hi 5 cn O CX] LO cn cn <o x ^H 00 00 00 00 00 00 00 00 00 01 H n AND ^S H ι — 1 O ft g 00 kO t — 1 00 l> ΟΊ O et UJ <o LO ΟΊ O 1 And Q. Φ CX] CX] cn CX] t — 1 CX] <o ç CX] 4-> 01 O Ο Λ cn t — 1 cn kO LO kO O LO u \ cn t — 1 cn <o cn t — 1 r * <o I P K K K K K K K K K The H O O O O O O O O t — 1 X 3 Γ— | tl < PQ u Q M H O H • d X ΟΊ ΟΊ ΟΊ ΟΊ M t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1 t — 1

107/126

r * ο

• 4-> η O Φ AND ΟΊ ç O ϊ — 1 CL CO O O CL κ u U Ο the X IXI AND Τ '* 3 M CL ΟΊ CO Γ— | Pm Q CL • CL η O IXI ΟΟ ç M CL 00 O Q κ u ο \ ° Ο the X CX] PQ AND ΟΊ 3 CL ΟΊ Γ— | Φ u CL H τ — 1 O CX] PQ Ε CO C0 β 0 u CM 4-> Φ u CL CL <Ο κ Ο The X .Al AND Ο 3 CL ο Γ— | Pm Φ u CL τ — 1 O ι — 1 AND C0 <Ο c o u t— 4-> Φ u CL CL <Ο κ Ο O LO H ΟΊ ç H AND Ο CX] CO AND O > ’ Λ Τ '* r — 1 The co Λ ι — 1 ΟΊ <Ο «Tf η ϊ — 1 CM O Λ ι — 1 <ο C0 «Tf η Γ- κ CM Ρ Τ '* u ι — 1 η • X ΟΊ M τ — 1

ok ω ω

01 1-1 AND Ο Ν Φ Ό 4-> Φ Φ tn + Ο Ο 1-1 ο m κ Ç Ç tn φ ι — 1 ο II φ Λ C φ s 1-1 Ο CL ι — 1 -Η 4-> φ tn Φ Ο φ Ό C Ό Ό O Φ ι — 1 ο 1-1 ο s 3 φ ίφ υ AND ω tn ι — 1 Ή 1-1 \ Φ ι — 1 φ O υ Ο > S-l CL Ç Φ ι — 1 Ο AND Φ φ υ Ή Ç Ό ι — 1 -Η φ O Μ-ι Ο Ό CL Ο * Φ Ο Ο Cn 4-> φ 4-> 3 Ό Ç Ό Ο φ Ο 1-1 υ Φ 1-1 CL -H CL 1-1 υ φ ο ç Ο Ό CL <φ Ç Φ ο -H υ AND X ω -H CL Φ Φ Mi CL 4-> CL Φ «Ό ¹ ιη LD r—

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108/126 ω Ο ί-ι Φ Ê Ή ι — I

Ο CL ω ο Ό ω Φ

108/126 Η α α F ί ς ί r

Φ Ό

Φ -Η

S-I ίλ Ο

S-I CL σ>

Φ ι — I

Φ Λ

Φ Η

CRYSTAF Peak Area (% w / w) 06 1 17 H Ê ω Q H o U H 06 1 31 TCRYSTAF (° C) 30 1 68 92 00 00 CD <d 6th H 120 118 120 Heat of Fusion (J / g) 26 26 00 c X i t — 1 K CX] O K CX] t — 1 K CX] ι — 1 ° s tn 64,800 66,900 69,400 ι — 1 s ° 5? tn 135,000 131,600 144,500 CM H o t — 1 H t — 1 K r * t — 1 K r * CX] K r * o t — 1 H 'xT kO O r * CD co CM H CD K O 1.0 LO K O Density (g / cm ³ ) CD 00 K O fr998 Ό Γ- Γ- ΟΟ K O Ex. 19g 7 PM

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Table 9A Average Index of Blocks for Polymers

Exemplary

Example Zn / C ₂ ² Medium BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62 Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3, 15 0.59

¹ Additional information regarding the calculation of block indices for various polymers as disclosed in US Patent Application Serial No. 11 / 376,835, entitled Ethylene-aOlefin Block Interpolymers filed on March 15, 2006, in the name of Colin IP Shan, Lonnie Hazlitt, et al., And assigned to Dow Global Technologies Inc., the disclosure of which is hereby incorporated in its entirety by reference.

² Zn / C2 * 1000 = (Zn feed current concentration) / (1000000) M _w of Zn / (total ethylene feed * (fractional ethylene conversion rate 1) / M _W ethylene) * 1000. Please note that Zn in Zn / C ₂ * 1000 refers to the amount of zinc in the diethyl zinc (TEN) used in the polymerization process, and C ₂ refers to the amount of ethylene used in the polymerization process.

[236] The following table describes the polypropylene designations used in the examples.

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Designation of Polypropylene POE-1 a propylene elastomer for special uses of high melt strength, 0.875 g / cm ³ , MI <0.5 at 190 ° C (I ₂ ), tg delta at 0.1 rad / s of 1.25, commercially available from The Dow Chemical Company. PP-2 PRO-FAX PF814 commercially available from Basell Polyolefins Inc., is a high-melting PP homopolymer for special uses, MFR 2.5 (230 ° C, g / 10 min), tg delta at 0.1 rad / s 1.3. PP-3 commercially available Daploy WB130HMS resin from Borealis, a propylene based polymer, structurally isomeric, MFR of 2.1 (230 ° C, g / 10 min), tg delta at 0.1 rad / s of 1.3. PP-4 PRO-FAX SR256M, a random extrusion grade copolymer of PP, MFR of 2 (230 ° C, g / 10 min), tg delta at 0.1 rad / s of 4.5, commercially available from Basell Polyolefins Inc. PP-5 D114.00 Performance Polymer Commercially available developmental from The Dow Chemical Company which is a polypropylene copolymer modified with azide with 14% ethylenepropylene rubber and a delta tg at 0.1 rad / s of 1.6. PP-6 D6D83K, random extrusion grade polypropylene copolymer, MR of 1.9 (230 ° C, g / 10 min), density 0.9 g / cm ³ , commercially available from The Dow Chemical Company.

Example 20 and Comparative Example L [238] Polymer compositions of example 20 and comparative example L were prepared by mixing the respective list of ingredients as shown in table 10 below. The ingredients were mixed to form example 20 and comparative example L by the following formulation method. The fusion mixing of the formulations was performed using a Coperion ZSK25 corroborative twin screw extruder with a medium shear set of threads. The conditions of the

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111/126 cylinder and matrix were set to 50 lb / hr, with the following zone temperatures: Zone 1 was 140 ° C, Zones 2-7 were 200 ° C, and zone 8, in the matrix was 180 ° C.

Table 10

Comparative Example L Example 20 POE-1 73, 1 0 PP-2 24.4 24.4 MB50-002 0, 5 0, 5 Americhem gray concentrate 2.0 2.0 OBC 0 73, 1

Note: MB50-002 is a formulation containing 50% ultra high molecular weight siloxane polymer dispersed in polyethylene homopolymer (LDPE) available from Dow Corning Corporation, Midland, MI; Americhem Gray Concentrate is a colorant from Americhem, Cuyahoga Falis, OH; and OBC is the example polymer 19k above which is an ethylene / a-olefin interpolymer having a density of 0.877 g / cm ³ and a melt index of 0.5 prepared according to the general preparation procedure for example polymer 19k above.

[239] Extruded sheets example 21 and comparative example

M were prepared from example 21 and comparative example L, respectively, by extrusion according to the following procedure. The pelletized formulated wire was extruded in a Killion extruder equipped with a 24 inch die. The matrix windows were adjusted to give leaves 40 mils thick. The sheet line operated at a speed of 3.6 feet / min. With upper, central and lower roller temperature of 40 ° C, 40 ° C and 30 ° C, respectively.

[240] The extruded sheets of example 21 and comparative example M were thermoformed into sheets at 160 ° C, 170 ° C,

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180 ° C, 190 ° C, 200 ° C, and 220 ° C, respectively, by the following procedure. The sheets were thermoformed using a Lamco thermoformer equipped with 12 heaters individually controlled by quartz, upper and lower. An infrared pyrometer was placed at the bottom of the greenhouse to monitor the leaf's surface temperature. The sheets were formed by vacuum forming on a male tool, at a designated temperature.

[241] Scratch resistance of extruded and thermoformed sheets was measured according to a modification of the Standard Test Method for Scratch Resistance Assessment of Polymeric and Plastic Coatings Using an ASTM D7027-05 Instrumented Scratching Machine. Scratch resistance was measured using a Texas A&M scratch test machine described in A new test methodology for evaluating scratch resistance of polymers, by Wong, G.T. Lim, Moyse, J.N. Reddy, and H.J. Sue, Wear, Vol. 256, p. 1214-1227 (2004), which is incorporated herein by reference.

[242] The scratch test machine is illustrated schematically in figure 11. The scratch test device is built with the ability to perform single pass, multiple pass, constant load, constant speed, increasing load and increasing speed with the potential to operate under various ambient temperatures. The scratch test unit comprises a servo driven motor that drives the scratching tip or stylus with constant or linearly varying speeds. For constant speeds, the stylus can move in a range from 0 to 400 mm / s. For speeds

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113/126 linearly increasing, the stylus can move from zero speed to a peak speed of 400 mm / s. A range of scratching stylets can be designed for the scratch tester to perform single stride and multiple stride tests. The standard scratching knife is a spherical tip 1 mm in diameter, comprised of Grade 10 steel or better. The test device is designed to conduct tests with load controlled spring loads, with a load range of 0 - 100 N and a load cell sensitivity of 0.01 N. The test device is also equipped with sensory functions and data acquisition to record vital test data during tests, such as the tangential force acting on the stylus with an accuracy of 0.1 N for a load range of up to 1000 N. Data acquired for depth, horizontal position and stylus speed are accurate to 5 pm, 10 µm / s, respectively. During the tests, the test data is fed to an external computer for storage and processing. Test parameters, such as scratch passes, scratch length, and ethylene speed, are controlled by an embedded microprocessor housed in an instrumentation unit.

[243] The modified ASTM D7027-05 test used here was conducted at approximately room temperature and 50% relative humidity using a scratch speed of 50 mm per second, a scratch length of 80 mm. The load was linearly increased from it20N The data collection rate was 1000 points per second. The scratch resistance data from example 21 and example

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Comparative 114/126 M are listed in Table 11A below. The data shows that the scratch resistance of example 21 is higher than that of comparative example M.

Table 11A

Ex. Comparative M Example 21 Load in the appearance of whitening by visible scratch 7 N None up to 20 N loading

[244] The digital images of the scratches were obtained using an EPSON Perfection 4990 PHOTO flatbed scanner. Using EPSON software, images were scanned in color using the

Home Mode with 1600 dpi resolution.

The samples were evaluated based on the point at which whiteness by tension or other significant surface damage was observed. To quantify the scratch resistance performance of these materials, the normal load in the occurrence of whitishness by scratch was reported.

[245] A digital image of example 21 and comparative example M after the scratch resistance test shows that example 21 does not show any sign of whitening until a load of 20 N, while comparative example M shows whitening by scratch with a load of 7 N. In addition, example 21 exhibits a significant reduction in the degree of visible damage throughout the scratch incident. Due to the penetration of the scratching stylet in the soft TPO skin, a slight change in brightness may be observed in the scratch of example 21, however no whitening due to physical scratch was observed.

[246] The gloss of extruded and thermoformed sheets was measured according to the following method. The brightness of the sheet at an angle of incidence of 60 ° was measured before and after

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115/126 thermoforming according to ASTM D2457.

[247] The brightness data for the samples are listed in Table 11B below. The data show that the brightness of the extruded and thermoformed sheets of example 21 is lower than that of comparative example M.

Table 11B

Example Comparative M Example 21 Initial brightness of the extruded sheet 68, 6 16, 7 Glow after thermoforming at 160 ° C 10, 9 3, 8 Glow after thermoforming at 170 ° C 9.5 3.9 Glow after thermoforming at 180 ° C 14.2 3.4 Glow after thermoforming at 190 ° C 11, 6 5.0 Gloss after thermoforming at 200 ° C - 4.2 Glow after thermoforming at 220 ° C 16, 0 4.4

[248] Light Reflected under Nomarski. Small pieces of approximately 10 mm each from example 21 and comparative example M were cut and placed on a glass slide. The slides were placed in a sprinkler coater and coated with a palladium gold plasma for approximately 30 seconds to increase reflectivity and adhesion to surfaces. An Olympus Vanox research microscope was used under reflected Nomarski interference contrast to make an image of the topographic surface of the leaves before and after heat treatment at 160 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° C and 220 ° C, respectively. Images (as shown in figures 8A-D) were captured using a 20X objective lens for each of the samples and digitally recorded using a Nikon DXM1200 digital camera.

[249] The micrographs of example 21 It's from example comparative M show what the leaves extruded and thermoformed of example 21 has surface patterns of greater

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116/126 comparatively thermoformed scale of the example larger scale of the sheets with extruded sheets and comparative M. These patterns in example 21 cause greater surface roughness (see the surface roughness data in tables 12-16 below). It was found that the greater the surface roughness, the lower the gloss. In fact, when comparing the extruded sample with the thermoformed sample (ie, comparing figures 8A with 8B and 8C with 8D), it can be seen that the size scale of these surface patterns in the optical micrographs increases after the heat treatment. be due to the increased roughness after heat treatment which leads to lower surface gloss.

[250] Electronic Transmission Microscopy. Injection molded bars of the polymer compositions example 20 and comparative example M were trimmed in such a way that sections could be collected on the skin and parallel to the orientation. The trimmed samples were cryo-polished before staining to remove sections of the blocks at less than 60 ° C to avoid soiling the elastomer phases. The polished cryo blocks were stained with the steam of a 2% aqueous solution of ruthenium tetroxide for 3 h at room temperature. The staining solution was prepared by weighing 0.2 g of ruthenium (III) chloride hydrate (RUCI3 x H ₂ O) in a glass bottle with a screw cap and adding 10 mL of 5.25% hypochlorite aqueous solution of sodium to the pot. The samples were placed in the glass jar using a glass slide having double-sided adhesive tape. The samples were placed face down on the skin of interest in such a way that the skin was protected by the tape. The slide was placed in the bottle in such a way as to suspend the blocks about 1

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117/126 inch above the staining solution. Sections approximately 100 nanometers thick were collected at room temperature using a diamond knife on a Leica EM UC6 microtome and placed on virgin 400-mesh TRAIN grids for observation. Images were collected on a JEOL JEM-1230 operated at 100kV accelerating voltage and collected on Gatan-791 and 794 digital cameras. The images were post-processed using Adobe Photoshop 7.0.

[251] Figures 9A and 9B show hard polypropylene domains dispersed in the ethylene / a-olefin interpolymer matrix which is characterized as a lamellar morphology associated with the chain-folded hard segment domains (arrows). In contrast, the polypropylene / POE-1 mixture shows that the polypropylene hard domains dispersed in the POE-1 matrix are characterized as a granular or fringed micelle morphology (figures 9C and D). After thermoforming, the lamellar structure in the ethylene / a-olefin interpolymer becomes coarser (figure 9B) and this is believed to contribute to the lower gloss observed in the ethylene / aolefin / polypropylene mixture.

[252] 2D profileometry. Profiling was obtained on a KLA-Tencor P-15 stylus profilometer using a diamond tip with a 2 pm radius (60 degree cone) and a 0.5 milligram load. 2D in-line profiles were collected as a sequence and aligned parallel to the extrusion direction. 5 mm lines have (10) been spaced 0.5 mm apart. Each line consisted of 2500 points sampled at 50 pts / sec (50 seconds per line). Line data was collected using a wavelength cutoff filter

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118/126 filter) with 800 pm in length. The raw line data is thus divided into two profiles: one for roughness and one for undulation (see figure 10). The surface roughness of example 21 and comparative example M before and after thermoforming are shown in tables 12-16 below.

[253] The profiling results in tables 12-16 showed that all the roughness parameters (Ra, Rq, Rzi ₀ , Rp, Coating) showed an increase following the thermoforming with the relative roughness quantity of the ethylene / interpolimer mixture. α-olefin / polypropylene being substantially greater than that of the polypropylene / PP 1 mixture.

Table 12

Ra (nm) Ex. Comp. M Ex. Comp. Μ (T) Example 21 Example 21 (T) Average 82.0 763, 1 512.4 2985.4 D. P. 19, 8 54.7 63.5 203, 0 Min. 59, 2 674.8 401, 4 2684.7 Max. 118.5 845, 8 603, 4 3402.7 Banner 59, 3 171, 0 202.0 718, 1

Note: Ra = arithmetic mean deviation from the absolute values of the roughness profile of the midline or central line. Also known as average center line roughness (CLA). The central line divides the profiles in such a way that all areas above it are equal to the areas below it.

Table 13

Rq (nm) Ex. Comp. M Ex. Comp. M (T) Example 21 Example 21 (T) Average 144.4 978.9 727.6 3698.9 D. P. 56, 8 89, 1 91, 4 232.2 Min. 88, 9 852.8 570, 0 3435.2 Max. 281, 9 1099.9 848.5 4249.5 Banner 193, 0 247.1 278.5 814.3

[254] Note: Rq = deviation from the minimum square root or geometric mean of the roughness profile from the midline

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119/126 measured in the sampling extent.

Table 14

Rzio (nm) Ex. Comp. M Ex. Comp. Μ (T) Example 21 Example 21 (T) Average 1064.6 5003.2 4471.8 16499.1 D. P. 325, 2 788.9 592.8 1124.8 Min. 674.1 4172.0 3526.5 15094.0 Max. 1740.1 6447.8 52532.6 18643.5 Banner 1065.9 2275.8 1706.1 3549.6

Note: Rzio = difference in average height between the 5 highest and 5 deepest valleys within the sampling extent measured from a parallel line to the midline.

Table 15

Rp (nm) Ex. Comp. M Ex. Comp. Μ (T) Example 21 Example 21 (T) Average 1097 3314 1713 10555 D. P. 757 1967 1352 1714 Min. 379 2043 778 8441 Max. 2444 8780 5077 13815 Banner 2066 6737 4299 5374

Note: Rp = the distance between the midline and the highest peak along the sampling extent.

Table 16

Rv (nm) Ex. Comp. M Ex. Comp. Μ (T) Example 21 Example 21 (T) Average 1019 3200 4488 10147 D. P. 594 546 926 1581 Min. 507 2301 3027 7891 Max. 2377 4082 6077 13294 Banner 1870 1781 3051 5403

Note: Rv = the distance between the midline and the deepest valley along the sampling extent.

Examples 22-25 [255] Example 22-25 polymer compositions were prepared by mixing the respective ingredient list shown in table 17 below. The ingredients were mixed to form examples 22-25 by the method of

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120/126 wording to follow. The fusion mixing of the formulations was carried out using a Coperion ZSC corrective double screw extruder equipped with a set of medium-shear threads. The cylinder and die conditions were set to 50 lb / h, with the following zone temperatures: Zone 1 was 140 ° C, Zones 2-7 were 200 ° C, and zone 8, in the matrix was 180 ° C.

Table 17

Example 22 Example 23 Example 24 Example 25 OBC 73, 1 73, 1 73, 1 73.1 PP-3 24.4 PP-6 24.4 PP-2 24.4 PP-5 24.4 Color 2.0 2.0 2.0 2.0 PDMS 0, 5 0, 5 0, 5 0, 5

Note: OBC is the example polymer 19k above which is an ethylene / a-olefin interpolymer having a density of 0.877 g / cm ³ and a melting index of 0.5 prepared according to the general preparation procedure for the example polymer 19k above.

[256] Extruded sheets of examples 225-25 were prepared by extrusion according to the following procedure. The pelletized formulated wire was extruded in a Killion extruder equipped with a 24 inch die. The matrix windows were adjusted to give leaves 40 mils thick. The sheet line operated at a speed of 3.6 feet / min. With upper, central and lower roller temperature of 40 ° C, 40 ° C and 30 ° C, respectively.

[257] The extruded sheets of examples 22-25 were thermoformed at sheets at 160 ° C, 170 ° C, 180 ° C, and 190 ° C by the following procedure. The sheets were thermoformed using a Lamco thermoformer equipped with 12 heaters

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121/126 individually controlled by quartz, upper and lower. An infrared pyrometer was placed at the bottom of the greenhouse to monitor the leaf's surface temperature. The sheets were formed by vacuum forming on a male tool, at a designated temperature.

[258] The brightness of the extruded and thermoformed sheets was measured according to the following method. The sheet brightness at an incidence angle of 60 ° was measured before and after thermoforming according to the ASTM D2457 standard. The brightness data (%) are listed in table 18 below. The data shows that the branched polypropylene exhibits a lower gloss.

Table 18

Example 22 Example 23 Example 24 Example 25 Extruded sheet initial brightness 3, 2 10, 6 3, 5 4.6 Glow after thermoforming at 160 ° C 3, 2 17.1 3.0 4.4 Glow after thermoforming at 170 ° C 2.9 21, 6 3.1 5.1 Glow after thermoforming at 180 ° C 2.7 21, 1 3, 2 4.8 Glow after thermoforming at 190 ° C 3.0 15, 7 3, 3 5.0

Comparative Examples P and T [259]

Comparative examples P and T were prepared by mixing the respective list of ingredients as shown in table 19 mixed to form the ones below. The ingredients were comparative examples P and T by the following formulation method. The fusion mixing of the formulations was performed using a Coperion ZSK25 corroborative twin screw extruder with a medium shear set of threads. The cylinder and die conditions were set to 50 lb / h, with the following zone temperatures: Zone 1 was 140 ° C, Zones 2-7 were 200 ° C, and zone 8, in the matrix was 180 ° C.

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122/126

Table 19

Ex. Comp. P Ex. Comp. T POE-1 73, 1 46, 9 PP-2 24.4 15, 6 CaCO ₃ 20 oil 15 Americhem gray concentrate 2 2 MB50-002 0, 5 0, 5

[260] Note: Americhem Gray Concentrate is an Americhem dye, Cuyahoga Falis, OH; MB50-002 is a formulation containing 50% ultra high molecular weight siloxane polymer dispersed in polyethylene homopolymer (LDPE) available from Dow Corning Corporation, Midland, MI.

[261] The comparative examples P and T were evaluated for physical properties such as the TMA penetration test, melt flow rates I ₂ and lio, Shore A hardness, density, tensile strength, machine direction elongation, tear strength in the direction of Matrix C machine, permanent compression deformation. The test results are shown in table 20.

Table 20

properties Ex. Comp. P Ex. Comp. t I ₂ at 190 ° C 0.45 1.58 lio at 190 ° C 12.82 36, 42 DSC Tcrystaf (° C) 133, 9 128 Penetration 1 mm - TMA (° C) 128.00 110 Cast resistance (cN) 8 6 Cast strength (mm / s) 160 175 Density (g / cm ³ ) 0.9 1.01 Shore A 84 74 TYrativa (DM, N / mm ² ) 6.7 3.7 Elongation (DM) 400 330 Tearing matrix C (DM) 38, 4 25, 2 Permanent compression strain (22 h at 25 ° C),% 39, 7 24.26

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123/126 [262] The complex viscosities of comparative examples P and T were also tested by the Rubber Process Analyzer (RPA-2000) from Alpha Technologies, Akron, OH. The test results are shown in table 21. The data shows that the complex viscosity (units of Pa.seconds) decreases with increasing shear rate (units of reciprocal seconds).

Table 21

Rate Ex. P Ex.T 0.01 74454 31987 0.02 44041 19288 0.03 40383 16551 0.05 32274 14602 0.15 16630 7266 0, 3 11122 5049 0.75 6497 3105 1, 51 4275 2096 3.01 2880 1495 7.53 1672 895 12.01 1266 705 15, 07 111 616 18, 04 998 564

[263] The capillary viscosity (units Pa.seconds) of comparative examples P and T at different shear rates (units of reciprocal seconds) was also measured by a capillary rheometer at 190 ° C. Capillary viscosity results are shown in table 22.

Table 22

Shear rate Ex. Comp. P Ex.Comp. T 99.9936 1099.24 978,099 149.99 887,534 496,804 249,984 669,315 326,694 399,974 509,925 247,333 630,029 377,035 188,053 1000.05 280,274 141,652 1500.02 216,167 105,931 2499.96 153,154 78.5195 3999.97 108,086 56.4835

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124/126

Examples 26-35 [264] Examples 26-35 were inventive polymer compositions prepared by melt blending the respective list of ingredients as shown in table 23 below. The fusion mixing of the formulations was carried out using a corrective double screw extruder equipped with a set of medium-shear threads.

Table 23

Ex. 33 Ex. Comp. T OBC, IF 0.5 46, 9 PP-2 MB50-002 0, 5 CaCO ₃ 20 Oil 15 Americhem gray concentrate 2

[265] Note: OBC is the example polymer 19k above which is an ethylene / a-olefin interpolymer having a density of 0.877 g / cm ³ and a melting index of 0.5 prepared according to the general preparation procedure for the example polymer 19k above; LDPE is a 6621 low density polyethylene having a melt index of 0.47 g / 10 in (ASTM D1238), a density of 0.919 g / cm ³ (ASTM D792) commercially available from The Dow Chemical Company, Midland, ΜΙ; MB50-002 is a pelletized formulation containing 50% ultra high molecular weight siloxane polymer dispersed in polyethylene homopolymer (LDPE) available from Dow Corning Corporation, Midland, MI; Americhem Gray Concentrate is a colorant from Americhem, Cuyahoga Falis, OH.

[266] Example 33 shows 4.4% brightness (60 degrees), while comparative example T shows 30% brightness, thus lowering (i.e., improving) the brightness of the inventive formulations.

[267] Examples 26-34 were tested for Tm and Tcrystaf as determined by scanning calorimetry.

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125/126 differential (DSC) as well as melt flow rates I ₂ and lio, density, Shore A hardness, tensile strength in the machine direction, elongation at break, tear resistance Matrix C in the machine direction, permanent compression deformation , brightness at 60 ° and pseudoplasticity index. The test results are shown in table 24 and table 25.

Table 24

Ex. 33 Ex. Comp. T DSC Tm (° C) 119/153 DSC Tcrystaf (° C) 107/122 I ₂ at 190 ° C 2.24 lio at 190 ° C 29, 34 Density (g / cm ³ ) 1.01 Shore A 73 Tractive (DM, N / mm ² ) 9, 33 Elongation at break (%) 925 Rip. Matrix C (DM, N / mm) 45.7 Deform. Perm. % (23h to 23 ° C) 33, 18 Brightness 60 ° (%) 4.4

[268] Example 29 and comparative example P were also tested for sheet gloss at 60 ° and sheet gloss at 60 ° after thermoforming at temperatures of 160 ° C, 170 ° C, 180 ° C, 190 ° C and 220 ° C. The results are shown in table 25.

Table 25

Ex. 2 9 Ex. Comp. P Leaf brightness at 60 ° 16, 7 68, 6 Leaf brightness at 60 ° after thermoforming at different temperatures 160 ° C 3, 8 10, 9 170 ° C 3.9 9.5 180 ° C 3.4 14.2 190 ° C 5 11, 6 220 ° C 4.4 16

[269] Extrusion profiles were made from a comparative example from Santoprene, example 32, and a comparative example T. Nomarski images reflected from surfaces

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126/126 of the extruded profiles are shown in figures 12-14, respectively. The images were obtained in a manner similar to that of example 21 and comparative example M described above. The micrographs show that the extrusion profile of example 32 shows larger scale surface patterns (and, hence, less brightness) compared to the comparative example T.

[270] While the invention has been described with respect to a limited number of embodiments, the specific characteristics of an embodiment should not be attributed to other embodiments of the invention. No individual embodiment is representative of all aspects of the invention. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned here. In other embodiments, the compositions or methods will not include, or be substantially free from, any compounds or steps not listed here. Variations and modifications of the described embodiments exist. Finally, any number published here should be understood as approximate, regardless of whether or not the word about or approximately is used in the description of the number. The attached claims are intended to cover all such modifications and variation while falling within the scope of the invention.

Claims (10)

1. Polymer composition, characterized by the fact that it comprises: (i) at least one ethylene / a-olefin interpolymer, the ethylene / a-olefin interpolymer being a multi-block ethylene / a-olefin interpolymer having one or more of the following properties before crosslinking: (a) an M _w / M _n of 1.7 to 3.5, at least one melting point, T _m , in degrees Celsius, and a density, d, in grams / cubic centimeter, with the numerical values of T _{m and} d correspond to the relation: T _m > -2002, 9 + 4538, 5 (d) - 2422.2 (d) ² ; or (b) an M _w / M _n of 1.7 to 3.5, and exhibit a heat of fusion, ΔΗ in J / g, and a delta quantity, ΔΤ, in degrees Celsius defined as the temperature difference between the highest DSC peak and highest CRYSTAF peak, with the values of ΔΤ and ΔΗ having the following relationships: Δτ> -0.1299 (Δη) + 62.81 for Δη greater than zero and up to 130 J / g, ΔΤ> 48 ° C for ΔΗ greater than 130 J / g, the peak of CRYSTAF being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the cumulative polymer has an identifiable peak, then the temperature CRYSTAF is 30 ° C; or (c) has an elastic recovery, Re, as a percentage of 300 percent elastic deformation and 1 cycle measured with a compression molded film of ethylene / a-olefin interpolymer, and a density d, in grams per cubic centimeter, and the numerical values of Re satisfy the following relationship, when the ethylene / a-olefin interpolymer is substantially phase-free Petition 870180058060, of 07/04/2018, p. 135/156 2/4 reticulated: Re> 1481 - 1629 (d); or (d) a comonomer content of a fraction by TREF that elutes between 40 ° C and 130 ° C, greater than or equal to the amount (0.2013) T + 21.07 where T is the numerical value of the elution temperature peak of the TREF fraction being compared, measured in ° C; or (e) a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° CG' (100 ° C), the ratio of G '(25 ° C) to G '(100 ° C) is from 1: 1 to 10: 1; (f) at least one molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, the fraction having a Block Index of at least 0.5 to 1 and a molecular weight distribution, M _w / M _n , greater than 1.3; or (g) an average Block Index greater than zero to 1.0 and a molecular weight distribution, M _w / M _n , greater than 1.3; and (ii) a polypropylene having a delta tg value at 0.1 radian per second of less than 2.5; and (iii) 0.1 wt% to 1.0 wt% of a polydialkylsiloxane of ultra-high molecular weight having an alkyl group CI_ _4. 2. Composition according to claim 1, characterized in that the ethylene / a-olefin interpolymer has an M _w / M _n of 1.7 to 3.5 in at least one melting point, T _m , in degrees Celsius, and a density, d, in grams / cubic centimeter, with the numerical values of T _{m and} d corresponding to the relationship: T _m > 858.91 - 1825.3 (d) + 1112.8 (d) ² . 3. Composition according to claim 1, characterized by the fact that the ethylene / a-olefin interpolymer is Petition 870180058060, of 07/04/2018, p. 136/156 3/4 defined by an elastic recovery, Re, in percentage to 300 percent elastic deformation and 1 cycle measured with a compression molded film of the ethylene / a-olefin interpolymer, and a density d, in grams per cubic centimeter, with the numerical Re values satisfying the following relationship, when the ethylene / a-olefin interpolymer is substantially free of crosslinked phase: Re> 1491 - 1629 (d). 4. Composition according to the claim 1, characterized by the fact that the ethylene / a-olefin interpolymer has at least one molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, with the fraction having a block index of at least 0.5 up until 1 and a molecular weight distribution, M _w / M _n , greater than 1.3. 5. Composition according to claim 1, characterized in that the ethylene / a-olefin interpolymer has an average block index greater than zero to 1.0 and a molecular weight distribution, M _w / M _n , greater than 1.3. Composition according to any one of claims 1 to 5, characterized in that the polypropylene has a delta tg value at 0.1 radian per second of less than 1.5. 7. Composition according to any of the claims 1 to 5, characterized by the fact that polypropylene has a delta tg value at 0.1 radian per second of less than 1.0. Composition according to any one of claims 1 to 5, characterized in that the polypropylene is selected from a branched polypropylene, a polypropylene having a melt strength of at least Petition 870180058060, of 07/04/2018, p. 137/156 4/4 5 cN at 100 mm / s, and a polypropylene having a melt flow rate of at least 0.5 g / 10 minutes measured with a load of 2.16 kg at 230 ° C according to ASTM D 1238. Composition according to any one of claims 1 to 5, characterized in that it additionally comprises at least one additive composition, the additive composition being selected from the group consisting of a colorant or pigment, a scratch-resistant agent or damage, a plasticizer, an oil, an antioxidant, a UV stabilizer, a filler, a lubricant, an anti-fog agent, a flow adjuvant, a coupling agent, a cross-linking agent, a nucleating agent, a surfactant, a solvent, a flame retardant, an antistatic agent, an antimicrobial, or a combination of these. 10. Thermoformed molded article, characterized by the fact that it is formed by the polymer composition, as defined in any one of claims 1 to 5, and that: (1) said thermoformed article has a gloss at 60 degrees on the surface of less than 9.0%; or (2) said article, after being submitted to ASTM D7027-05, at a load equal to or less than 2 0 N, and at a scratch speed of 50 mm / s, does not exhibit any whitening by substantial scratch on its surface ; and (3) can be both (1) and (2).